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1. deprecated if the data are highly suspicious There is one exception the sign of pK and log K values will be reversed if it is obvious that they are wrong due to misprints II 13 e How to deal with obviously identical data probably originating from the same source but not cited correctly Here there are two ways to proceed a store data record as published but with an appropriate comment or b correct add the data source but give an explanation in the comment e How to deal with literature references without any usable information Put a short description of the content in the comment field adding that there are no information directly usable for the database Just deleting that reference may lead to a later re occurrence especially if the title suggests that there may be useful information in it Furthermore set the status field to irrelevant e How to deal with values covering various ionic strengths IS If experiments for various ionic strengths are reported specify the lowest one in this field and mention the other ones in the comment field values and respective ionic strength If the reported protolysis constants refer to an extrapolated infinite di lution set the ionic strength to zero and specify all experimental ionic strengths in the comment field Leave the ionic strength field blank if the extrapolation to IS 0 is not explicitly given or if the work covers different ionic strengths and the published valu
2. I 32 The final data set can be exported into an ASCII file to be used in other geochemical speciation codes such as MINTEQA2 Allison et al 1991 GEMS Karpov et al 1997 PHREEQC PHREEQC 2 Parkhurst 1995 Parkhurst and Appelo 1999 or HARPHRQ Brown et al 1988 and reactive transport software such as CHEMTARD Bennet et al 1992 or OS3D GIMRT Steefel and Yabusaki 1995 Actually this is possible as Excel spread sheet or ASCII file 5 3 Data Input and Editing To prevent unauthorized data manipulation and the emergence of different unsynchro nized database versions the whole editing shell can be uncoupled and hidden from the USer To ensure that all lists for input selections are properly set up during the data input pro cedure a certain input order should be followed starting with the input or update of bib liographic data if not already correctly present Next step would be to add the mineral if it is still missing Then comes the input of sample specific data which in turn is a pre requisite for records containing site densities and surface protolysis constants Finally surface complexation data can be edited The menu Advanced Editing combines input masks for all auxiliary information that usually is not changed very frequently e SCM Theory e Experimental Methods Species Spectroscopic Evidence not used so far e Ligand Definition e Surface Site Types Mineral Alteration and Kinetics no
3. MS Windows 98 NT 4 or 2000 So far the RES T database has been successfully tested under the Microsoft operating systems Windows NT 4 Windows 2000 and Windows 98 In principle it should also work under Windows 95 Windows ME and Windows XP Any information about installations on these latter three platforms are very much appreciated At the moment the database can only be used when there is already MS Access 2000 part of the respective MS Office Professional Versions but also available separately installed on your PC After this has been confirmed the installation can start II 9 2 3 Program Setup There is no setup file so all steps must be done by hand All the files from the CD should simply be copied to a directory of your choice If you received a compressed zip archive expand it into a directory In any case pre serve the subdirectory structure Then right click on the file RES3T_2000 mdb select Properties and un check the Read only button most probably only set for the CD version The next step is to get the user authorization running With the default MS Access permission levels you will not be able to use RES T so you must make use of the RES3T_Group mdw file instead The easiest way to run RES T with the right per missions is to create a separate link on your desktop with the following target see link properties sheet Path to Access executable Path to RES T database Wrkgrp Path
4. quartz REST List of Mineral Surface Data for Quartz t Specific Surface Reported Literature Area m m 7g Grain Size in pm Heference 0 01 75 150 FICHEBMHOZ i 106 180 T gt lu E abli 5 BPTA36 ri J 150 250 r 125 250 r 53 200 r H 200 700 P REDCOOO rl 106 180 r lt 2 0 5 T Y 0 oo El ml 7 qi al 0 en Sm co co EB el al T98 u el be el cl be Fig 3 Query results of surface data for Ea Quartz Datensatz lA 4 1 i vor 51 4 1 2 Site Density amp Protolysis Pressing the button Site Density Protolysis will list all data records containing sur face binding site densities and site protolysis constants for the selected mineral The columns are from left to right Site Type Site Density in sites nm pK1 II 17 Exp Norm pK2 Exp Norm PZC C1 SCM Type and Literature Reference sorted by the SCM type and the literature reference code Fig 4 shows the query re sults of site density and surface protolysis data for quartz All site density values presented are already converted from the original unit into sites nm If one is interested in the originally published value a double click on the D but ton located right to the C1 column will lead to the respective detailed data record lag K af 1st deprotonation s OH2 0H H pke log K of nd deprotonatio
5. 0 mol L of NaND3 Ci 13 CH 2 Solid Liquid Ratio g L SCH Type Triple Layer r Fit Method graphic extrapolation z Add Edit Site Data Sue ee Dota Surface Site Density Protolysis Constants Experimental Methods Tritium Exchange Potentiometric Titral Type in sites nm 2 suri pki KT pK2 Comment citation in 2594 also other value for pz 6 8 cited from 7205 30 double extrapolation technique to tonic strength same values Far background electrolvte Mall Internal Status Details Last Modification at 10 08 2004 10 26 40 by anke Fig 18 Input and RT editing form for site 5 UN Zi density and surface protolysis data Datensatz 14 4 li bn gt von 1050 Mineral Select from a scroll list if not available go back to the input mask Mineral and add the respective mineral See there for further details Original Publication Select from a scroll list if not available go back to the input mask Publication and add the respective paper See there for further details Citation in If information is only cited in a secondary data reference add this citing paper If later access to the original reference is available clear the citation entry and move the information about citation s into the comment field Specific Surface Area Reference to the used specific surface area SSA either the same work or taken from another publication Select from a scr
6. 12 05 norm P exp 8 norm These normalized values are shown accordingly in the columns labeled with pK Norm next to the original value corresponding to the experimental site density II 18 4 1 3 Surface Complex Formation Surface Complex Formation for a selected SCM The respective button is only activated when both a valid mineral and a valid surface complexation model is selected It lists all data records containing surface complex formation constants for the selected combination of SCM and mineral The columns are from left to right 1st Ligand Chemical Equation log K Exp Norm and Litera ture Reference sorted by ligand formula and reaction equation As for the Site Den sity amp Protolysis form the columns for log K correspond to the experimental value and the one normalized to a site density of 12 05 sites nm exp 12 05 logK log K x log The query results of surface complexation data for quartz with the Triple Layer Model are shown in Fig 5 RES T List of Surface Complexation Data for Quarz EJ with the Triple Layer t Sch 1st Chemical log E Literature Ligand Equation Exp Norm Reference EIS 2 sot0H Cac2 gt s5i 2 LCa 2 H lt 1 gt 250 2 30 r H34 junz2 r z55r0 0 54 UD2 2 4H2CO3 H20 52 0 002 04C03 19 00 19 42 r Kn2b Nade r s5HD 05H Nacte 510 0 5 Na Hee 740 7 82 r k02b N xdo r s5iD 0 54 NO3CI He1 gt s
7. 25i doubly 7 Stoichiometric 1 Coefficient Site Type Stoichiometric 1 Coefficient Site Type 1M Stoichiometric 1 Coefficient 0 y S Fig 24 Advanced Editing form for the Datensatz Wf 6 rtr von 6 Gefitert site types of minerals Mineral Select from scroll list If the required mineral is not available yet go to the in put mask Mineral and add the respective mineral See there for further details Once a mineral is selected all site types associated so far to this mineral are listed Site Type Select from a scroll list Only entries relevant for the afore selected mineral are listed The generic site types X OH X w OH X s OH and Y OH should only be used when it is not clear which site type is meant by the authors Most often this happens when dealing with clay minerals and not distinguishing aluminol and silanol sites If a required site type is not available yet it has to be added directly to the table SiteType there is no separate input mask Then the Update button of the Site Types form must be pushed to propagate the changes to this form Coefficient Select from scroll list The value gives the number of surface sites per for mula unit of the mineral II 44 6 6 6 Mineral Alteration and Kinetics This menu offers a possibility to enter information about chemical reactions forming dissolving or altering minerals including both thermodynamic and kin
8. A detailed description of the database RES T is provided within in the accompanying document RES T Manual Therefore only a short overview of the different menus is given here 5 1 Data Query and View Users can easily extract specific data sets e g all records relevant for the combination of a specific mineral and a specific SCM They can also choose to show all sorption data available for a certain element ligand ion or all published surface area data of a mineral Once a data set has been generated based on queries it can be shown on the screen or printed out as a well formatted report The results can also be exported into MS Excel spreadsheets for further processing In the Query menu double clicking into a scroll list field after a valid selection will give access to all details of the respective data item Such a more detailed look at data items is also provided in the various query result view forms here the small buttons la beled with D on the right hand side of the result fields 9 2 Data Assembly and Formatting According to the complexity of natural systems the user is given an opportunity to not only scan for a single mineral or ligand but to assemble a SCM data set for all combi nations of a list of chosen minerals and a list of chosen ligands In subsequent steps an SCM submodel must be selected to enforce at least a minimum degree of internal data consistency and the data set can then be further refined
9. Goethite 496 120 617 1088 323 FeOH Ck Fedde Hae AWJSSb Loc Goethe 496 120 amp 17 1088 1311 Fe 0H Cde2 gt H20 Fe0 CdH 2 HcTe AWJSSb fcc fGoethte 486 120 617 1088 356 XOH Co2 X0 Co H AwJ99b fcc Bee 436 120 617 1088 11 74 XOH Co2 H20 X0 CoDH 2H AwJ99b Ejec Fenhydte 182 354 607 363 357 Fe0H Pb2 2H20 Fe OH is PIOH2 FDM8S Loc JFemtydite 182 354 607 383 073 Fe0H 202 2H20 Fe0m3 Zn OH2 F FDM8S Ejec Femhydite 182 354 607 363 033 Fe0H Cd2 2H20 Fe OH s CdIOH2 FDM8S Fia 12 Global L Hec reuhedue 1821 3501 607 1 3531 157 eH Os 2420 Fela sl Cul E TEDMB Ig 12 GIODA i overview and x Selection of SCM Type 1 Baia collection Datensatz i 4 1 gt r von 210 4 5 4 Final Data Selection Based on the above made user decisions as an example the DDL model was se lected the remaining set of data records is shown with the following fields from left to right mineral specific surface area site density protolysis constants chemical equa tion delivering also information about the ligand surface complex formation constant and literature reference The table is sorted by literature reference code and mineral name see Fig 13 All constants are normalized to the reference site density Now the user can check using the boxes on the far right side of the table which of th
10. Names are separated by commas each family name is followed after a space by the surnames abbreviated to their first letter and with no space or punctua tion between the surnames Examples MacNaughton MG Garcia Delgado RA Garcia Herruzo F Title Title of the publication without any enclosing quotation marks Year Year of the publication Ph D thesis sometimes appear with year of delivery Mnemonic Code This field represents an abbreviated code mnemonic acronym for the bibliographic record Each entry must be unique It is constructed from the first letter of each of the up to five first authors followed by the two trailing numbers of the publica tion year and optionally a small letter to distinguish otherwise identical codes starting with a Examples CCEO2 S87a TZSNE99 Pages First and last page of the publication connected with a hyphen In case of books it is also possible to enter the number of pages directly followed by pp Examples 124 135 346pp Type Type of the publication select from a scroll list This list is stored in the table PaperType A direct editing in this table is however not recommended because sev eral interface procedures use code specific to each paper type Currently the paper types already include Article Book Chapter in Book Proceedings Internal Report Chapter in Report Personal Communication Ph D Thesis M Sc Thesis WWW link URL Patent Norm Standard This should cove
11. amongst ligands i n NpO CO Zn ba co N The distribution of the log K data records in terms of actinides fission and activation products is shown in Fig 12 As can be seen most of the relevant records currently contained in the database are surface complexation constants for uranium VI In gen eral there is a lack of data for the reduced oxidation states of U Np and Pu This means that at present the information supply is very unbalanced concerning the re quirements of risk assessment and site remediation in the nuclear field I 30 UO2 lt 2 gt NpO2 lt 1 gt Th lt 4 gt Am lt 3 gt Pu lt 4 gt PuO2 lt 2 gt PuO2 lt 2 gt NpO2 lt 2 gt Np lt 4 gt U lt 4 gt Np lt 3 gt Pu lt 3 gt Pb lt 2 gt Ni lt 2 gt Co lt 2 gt Fe lt 2 gt Eu lt 3 gt Sr lt 2 gt SeO3 lt 2 gt Cs lt 1 gt Ra lt 2 gt Eu lt 2 gt Pm lt 3 gt I lt 1 gt SbO OH 4 lt 1 gt Fe lt 3 gt Ligand Number of Data Records 100 200 242 I 31 Fig 12 Amount of surface complexation constants for actinides and relevant fission activation products 5 Description of the Database The Start Menu Main Menu opens after starting RES T following brief information about some local program settings By clicking on the buttons e Data Query amp View e Data Assembly amp Formatting e Data Input amp Editing e Administration e General Help the corresponding menus will be opened
12. e g in Ticknor and R egger 1989 or Petschel et al 1995 Though the US EPA report of Wilhelm and Beam 1999 con tains in addition to Ky values some SCM parameters the selection of data is restricted and there are no possibilities for user interaction and coupling to speciation software in the printed form Recently there has been published a digitized version of a sorption database by Brasser et al 2002 focusing on distribution coefficients for chemical toxic contaminants and soils The lack of a thermodynamic sorption database has various consequences e A systematic identification and closing of data gaps becomes very difficult e A critical data survey rarely takes place Hence recommended value sets as necessary for comparisons of different sorption experiments and sorption mod eling do not exist e the compilation of problem oriented data sets from the primary literature needs large effort Thus they may be incomplete whereas the selection criteria are of ten hard to understand by third parties e Occasionally even the use of inconsistent data sets for sorption models can be observed e g the utilization of data of amorphous glass for the description of quartz or the mixture of data based on different SCM concepts e Sorption and based on this migration modeling results can therefore exhibit large uncertainties or plain errors whereby the acceptance of the intrinsically progressive SCM concept is lessened
13. no mica carbonates others 4 3 Sample Specific Data The database comprises nearly 900 data sets of sample specific data sample origin preparation steps and analytical results characterizing the samples used in sorption experiments Fig 7 shows the distribution of specific surface area data records refer ring to minerals RES T database Distribution of specific surface area data records Others Vernadite amorphous Anatase Silica Rutile Corundum Gibbsite Haematite Magnetite Illite Ferrihydrite S Alumna Fig f Distribution of Montmorillonite Quartz specific surface area data records Kaolinite 4 4 Site Density and Surface Protolysis The distribution of more than thousand protolysis data records with respect to the min erals is shown in Fig 8 Concerning the solid phases iron hydr oxides clays alumi num hydr oxides quartz varieties and manganese hydr oxides are well represented whereas important rock forming mineral groups such as feldspars mica pyroxenes amphiboles or olivines have not been investigated to a satisfactory extent l 28 RES T database Distribution of protolysis data records Others Goethite Haematite amorphous Silica Magnetite Anatase Fig 8 Distribution of Corundum Kaolinite Rutile Ferrihydrite protolysis data records referring to minerals 4 5 Surface Complex Formation About 2600 data records of surface complex formation
14. 2 Statistical Data Evaluation u a 46 7 3 Set Reference OM 47 7 4 Set Manual Path 47 7 5 EXDOEUTO MV SO Larena E 48 7 6 Reload Local Options RN 48 9 GENERAL VE Pe A Ranger 50 9 ACKNOWLEDGEMEN Tirana 50 10 CONTACT Sana 50 11 REFERENCES M E NE E eM EE MEE EM EE EVE 51 II 4 List of Tables Table 1 Navigati n OUT ONS sa ee eier List of Figures Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig pee m a 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Main menu of the database RES T sssse eee Data Query amp View menu of the RES T database eeeee Query results of surface data for Quartz usse Positioning of ions and correlation between charge and potential for the Basic Stein Model ernst Internal relationships and content of the data tables of RESTT Query results of surface complexation data for Quartz with UO Query results summarizing surface complexation data for Quartz Query results of data references of DaviS cccccceeeeeeeeeneee eens Data Assembly amp Formatting menu of the RES T database Selection OF mineral uta a Ra OP Ut da SEIECIHON OLIIGANGS zusenden Global overview and data collection ooooccccccccccnconcnnccnocnnncnnnos FINAl Gata
15. Brendler G Bernhard The mineral specific sorption database REST Concept description implementation and application towards contaminated systems Goldschmidt Conference 2003 September 7 12 2003 Kurashiki Japan and Geochimica et Cosmochimica Acta 67 2003 A397 e V Brendler T Arnold A Richter G Bernhard Capability of surface complexation models and databases for predicting radionuclide sorption Waste Management Con ference 04 Tucson Arizona February 29 March 4 2004 e A Richter V Brendler Capability of SCM and RES T database for blind prediction SOPRO 2004 International workshop on sorption processes at oxide and carbonate mineral water interfaces Karlsruhe March 25 26 2004 and SOPRO 2004 Book of extended abstracts Wissenschaftliche Berichte FZKA 6986 June 2004 p 127 131 e V Brendler A Richter N Baumann T Arnold Characterization of surface species and development of a sorption database ENSCP seminar Paris April 28 2004 e A Richter V Brendler C Nebelung Blind prediction of Cu II sorption onto goethite Current capabilities of surface complexation modeling Geochimica et Cosmochimica Acta submitted 2004 e A Richter V Brendler C Nebelung The effect of parameter uncertainty on blind prediction of Np V sorption onto hematite using surface complexation modelling NRC 6 Sixth International Conference on Nuclear and Radiochemistry Aachen Germany August 29 September 3 2004
16. DDL f ma r 5r0H Ame3 gt s5rD Amc2e Hoe 435 r jw r db n l NE r uBz2e r sSiwFOH U02 lt 2 gt H20 5ipwrO LU D 2 0H 5 32 r DKON ni NE rose r sSipsHOH UD2 2e H20 sSilw O U02 0H 5 28 6 56 r DEO n INE r unz2e r sSiskOH U02 lt 24 gt H20 sSis 0 JO2 0H 256 5 60 DKO n Fig 7 Query results PINE elfos r ssiwE H 0002 lt 2 H2C03 ssipo unecr 6 501 7 78 riok n summarizing surface complexation data for Quartz I qi JI n2 co Pa LI qi Datensatz 141 4 ete von 97 11 20 4 2 Publications The query field can contain either part of the name of an author or part of a mnemonic literature reference code An asterisk can be used as wildcard for the search string The columns of the result list are from left to right Reference Code Author s Ti tle below the authors and Year sorted by the literature reference code Below the reference code the hard copy number is shown but this is for internal use only and may be removed later Fig 8 shows the query results for the author Davis RES T Selected Data References search string was ars Reference Author s Year Code Fe b ERA Arai Y Sparks LD Davis JA 2004 Zech or Sed Cais enden ae lan ao Seatac Soascuie ar ie tes BRADO1 Bargar JA Reitmeyer A Davis JA BEEN 2001 k aca AITAN af U vato surface CORIA ao Peas am an Bargar JA Reitmever A
17. Davis JA 1993 L SPECTET conan av waniey cad evan acho cantes cn DANDANE Bargar JA Fieitmeyer A Lenhart JJ Davis JA Vi Pace ar Hd stc ferr ana eva eae FD ES an ebria e Curtis GP Davis JA Kohler M Kent DB c Anke ec dat etatem ara a ASET TUS made ERA y CostonJA Fuller CC Davis ooo Y18515 Fe LAA oic Y a Pu N arae ova erg STE DRAUF Curtis GP Fox P Kohler M Davis JA 2002 k Y15660 AAA ey He raum A eae ae tace CORRA ION eis Curtis GC Fox P Kohler M and Davis JA 2004 Cc OSG ovo wt Gr uem A oae Nee OSA IS CORSA x E Surface Area a A Site Density 7 Protolysis EM Complex Formation Fig 8 Query results of data references of t H 5 Datensatz 14 4 e etl von 57 Davis Marking an entry from the list of search results allows to check for parameter sets stemming from that very source namely records for specific surface areas for site densities 4 protolysis constants or for surface complexation constants This is per formed by pressing the respective smaller buttons in the middle of the form footer 11 21 5 Data Assembly amp Formatting According to the complexity of natural systems the user is given an opportunity to not only scan for a single mineral or ligand but to assemble a SCM data set for all combinations of a list of chosen minerals and a list of chosen ligands In subsequent steps after screening the overall available data r
18. Do not use the full directory path as in contrary is required for all file export features The manual provides you more detailed information how to use RES T But keep in mind that the functionality offered by RES T is defined by the user permissions i e several features will be disabled especially administrative tasks and all data editing if you log in as a general user not belonging to the administrator group It is required that you start RES T from within the installation directory otherwise the manual pages will not be found by RES T If you create a shortcut link to RES T on your desktop be sure to set the working directory in the Properties field for this shortcut accordingly To uninstall the software it is sufficient to delete all the files that were copied from the RES T CD ROM or extracted from the zip file II 11 3 Start Menu Main Menu In Fig 1 you see the main menu that pops up after starting RES T But before this start menu opens a message box is shown informing about the current settings of the local options The following general navigation principles apply to all forms and menus being part of the RES T interface e f one wants to select an entry from a scroll down list the typing of one or more leading letters will scroll the list to the first matching entry e Entries are not case sensitive in all input fields for search queries and in scroll down lists e When the mouse moves over buttons an
19. European wide effort has to be launched 6 5 Publications The following publications and conference talks are summarizing results from the REST project e V Brendler A Vahle Th Arnold G Bernhard Th Fangh nel A mineral specific thermodynamic sorption database Migration 2001 Conference Bregenz Austria September 16 21 2001 e V Brendler T Arnold A Richter G Bernhard Th Fangh nel RES T Rossendorf expert system for surface and sorption thermodynamics 23 Rare Earth Research Conference Davis California July 14 18 2002 e V Brendler T Arnold A Richter G Bernhard Th Fangh nel From Kp to SCM Present state of actinide data supply International Conference and Workshop Ura nium Mining and Hydrogeology III Freiberg September 15 21 2002 e V Brendler T Arnold A Richter Current predictive capabilities of surface complexa tion models Annual Report FZR 2002 p 40 e V Brendler A Vahle T Arnold G Bernhard T Fangh nel RES T Rossendorf expert system for surface and sorption thermodynamics Journal of Contaminant Hy drology 61 2003 281 291 e V Brendler T Arnold A Richter G Bernhard Capability of surface complexation models and databases for predicting radionuclide sorption Migration 2003 Gyeongju Korea September 21 26 2003 I 39 e A Richter V Brendler Blind Prediction of Copper ll Sorption onto Goethite Annual Report FZR 2003 p 42 e A Richter V
20. SCle COM rt een tears bape tienes Data Input amp Editing menu of the REST database eese Input and editing form for publication data here article in a journal Input and editing form for mineral data ocoocccccccccccncnconcnonananoso Input and editing form for sample specific data Input and editing form for site density and surface protolysis data Input and editing form for surface complex formation Advanced Editing menu of the RES T database ceeee Advanced Editing form for the SCM theory Leesseeeseeses Advanced Editing form for the experimental methods Advanced Editing form for the ligand definition Advanced Editing form for the site types of minerals Administration menu of the RES T database II 5 II 6 1 Introduction RES T is a digitized version of a thermodynamic sorption database as required for the parametrization of Surface Complexation Models SCM It is mineral specific and can therefore also be used for additive models of more complex solid phases such as rocks or soils An integrated user interface helps to access selected mineral and sorption data to convert parameter units to extract internally consistent data sets for sorption modeling and to export them into formats suitable for othe
21. already included in RES T If a site density unit is not available it can be added in the table SiteUnit there is no extra input mask available But then also the respective unit conversion routine must be added to the query QPro tolysis Comment Additional remarks about the origin quality processing of data or about other citations of the same data This includes specification of ionic strength source of values other temperatures validity of parameters inconsistencies etc 6 5 Surface Complex Formation The form see Fig 19 manages the data records for all surface complex formation reactions It is thus the core of the RES T database II 36 Mineral Quartz Original Publication MZST95 Citation in SCH Type Triple Layer Site Protolysis Reference R82 1st nd Site Type Ligands un2 2 5 0H Coefficients 1 HEI T Equation 35i 0H UD 2 2 s5 ED HD2 1 H1 log K 0146 Propozal for Equation Fit Method FITEQL Ligand is Itself Experiment Batch Sorption Experiments r Background Electrolyte 7 lon c Strength 0 001 mol FL of MNaCciO4 r Aman Cation log K References for Electrolyte Faz r Comment lonic strengths 0 001 0 01 and 0 1 M Internal Status Details Last Modification at 10 08 2004 10 39 40 by anke Fig 19 Input and 8 la 2 a editing form for E surface complex Datensatz 14 4 5 r r
22. base equilibria of pure oxidic surfaces is insufficient when using a Non Electrostatic Model whereas equilibria of clays can be described more success I 20 fully Davis et al 1993 argued that this model may be the most appropriate model for complex environmental applications because the surface charging behavior of non ideal nature mineral phases is not well known 1 21 3 Design of the Database 3 1 Structural Design amp Implementation The database is designed as a Relational Data Base System RDBS All information is structured into logical subunits stored into separate tables which are logically con nected by the RDBS This ensures that every piece of information is only stored once Other benefits are high efficiency and internal consistency In Fig 5 a sketch of the major tables their data elements and their mutual relationships is given The modular design also eases later extensions such as inclusions of surface complexes with or ganics e g humic acids or interactions between surfaces and living matter e g mi crobes The database is implemented in Microsoft Access on PC providing an integrated graphical development system together with the RDBS Data records can be displayed as tables in forms or reports Possible data types are numeric logic text binary ob ject Queries to the database can be performed with the standardized Structured Query Language SQL opening the opportunity to access externa
23. button can be pressed 11 24 SCH Mineral Area in Sites normalized Chemical Literature Type m g nm pK 1 pK2 logk Equation Reference 3i K BS Ferihydrite 382 Jf 2sFe0H Zn lt 2 gt H20 Fe 0 2n0H2 lt 1 gt 2H 1 DM86 wkss remdiee 332 T 2 FeO0H Cd2s H20 Fe 0 Cd0H2 lt 1 gt 2H lt 1 gt M86 ik8s JHaematite 636 1000 82 1338 FeOH 05 Co lt 2 gt 2H20 FeOH CofOH 2 05 2 GJEAAD0 ik8s JHaematite 6536 10007 82 662 foreOH 05 Co lt 2s FeOHCo15 BJEAADO Jipk 8S remdie 182 foFesimayO0H1 2 Cd lt 2s H20 oF e singly OH Cd OH VDKB87 fk8s Haem e 2655 bFesnay0HU2 C26 H20 sFe singlOH Cd 0H VOKBE7 ik8s Boee 600 so 620 f Fe0H1 2 Cd lt 28 Fe DH Cd3 2 VHVS6a s Feriae 182 J2Fe0H zm29 H20 sFeOZnOH2cT gt 2 Her JDM88 fes Jjrswde 182 J FreO0HXxteCd2e H20 Fe 0 CdDH2 lt 1 gt 2H lt DM86 s Femhydite 182 LFe0H CdGe H20 sFeO CdDH HcTe VDKBB Jes Heme 265 oFe OH Cake H20 FeocdoH Hce VDKB87 Jes fGoethte 420 amp e amp 554 FeOH Cd2e Fe 0 Co lt 1 gt H lt 1 gt VHV96a Jes Goethite 420 ess X 55 4 FeO0H Cd2e sFe ckin Hin Jvnvssa ec Fewhydite 183 2700 535 305 273 FeOH Ck Fedde Hae ABS b ec Feriae 183 2700 535 905 233 FeOH 2n2s sFeOZnde Hae ABSOb Efes
24. form for the experimental methods Datensatz 14 4 z7 en r von 21 11 41 Technique Name of the experimental method Major Reference s Important publications dealing with the experimental technique i e development of the theory extensions major applications limitations etc The table shows the literature reference code authors and title of the publications Add Edit References The button will open an additional form Literature Experimen tal Methods with the fields Experiment which defaults to the experimental technique specified in the calling form Reference where a publication reference code can be selected from a scroll list and Comments a place for any additional remarks Used to Derive Several check boxes indicating whether an experimental technique is suitable for the determination of specific surface areas surface site densities pro tolysis constants complex formation constants or for a proof of existence of a surface species Comment Short description of the method and additional remarks about theoretical aspects application limits etc 6 6 3 Species Spectroscopic Evidence This menu offers a possibility to enter information about independent spectroscopic evi dence for surface species At present there are no data records provided so it is up to the user to build his own database Formula Chemical formula of the surface complex species Structure Proposed c
25. from a scroll list If a supplier is not available it can be added directly in the table Supplier there is no extra input mask available Sample Name Name of a commercial product or a natural product from a depository Select from a scroll list If a sample name is not available it can be added in the table SampleName there is no extra input mask available Preparation Preparation processing details including literature references Area Size Input of the SSA Specific Surface Area in m g with its associated error Experiment Method for the determination of SSA select from a scroll list If not avail able go back to Advanced Editing and add the respective method under Experimen tal Method See there for details Grain Size in um can also be a range or upper lower limit lt gt Comment Additional remarks such as details about the method of SSA determination e g No or Ar or Kr BET uncertainty of SSA determination comparison with refer ence data and with data of un treated samples assessment of the value analytical phase verifications purity etc 6 4 Site Density amp Surface Protolysis This form see Fig 18 contains all data about the surface binding sites their type density surface concentration and protolysis constants 11 33 Mineral Quartz Original Publication Ree Citation in Specific Surface Area 4 15 gt mig PZC 3 Capascmances Fm lon c Strength
26. g GRS Braunschweig PSI Villigen FZ Karlsruhe so user interests could be considered through direct feedback from the very beginning To further promote RES T the database concept realization and application was in troduced at various national and international conferences Though then the database was still in a preliminary stage the response by potential users was nevertheless very encouraging I 10 2 Models for the Description of Sorption Phenomena 2 1 Fundamentals There are many attempts in the literature to describe the interactions between ions in solution and a mineral surface in contact with them These interactions can be grouped into various phenomena such as physisorption chemisorption co precipitation inclu sion diffusion surface precipitation or even formation of solid solutions Surface com plexation in a strict sense only describes the chemisorption and has therefore to be combined with models for the other effects to ensure a proper thermodynamically based speciation model for the elements of interest Nevertheless on shorter time scales it is often the dominating process having a fast kinetics Processes such as dif fusion of sorbed ions into the host mineral and the subsequent formation of mixed crys tals or solid solutions may then follow but they require much more time This chapter briefly explains the models most often applied in sorption chemistry Much more de tailed information can be obtai
27. nf 226 6 56 9 66 n sFe wHOH NIEDTA lt 2 gt H lt 1 gt Felw EDTANi1 gt H 7 65 r BKECS4 56 9 66 n sFe wHOH Nic2 gt EDTA lt 4 gt H lt 1 gt Felw NiEDTA 28 03 rBKECS4 1 2 917 nf Fe 0H Co lt 2 gt Fe 0 Coc1 gt H lt 1 gt 6 00 r C96 1 2 feFe OH Co lt 2 gt H20 Fe 0 Co DH 2 H lt 1 gt 14 20 rfc B 11 26 n sFe s OH Pb lt 2 gt Fels 0 Pb lt 1 gt H lt 1 gt 2 32 rJDM30 600 00 n B 11 26 ni gt Fe s OH Zn lt 2 gt Fels 0 Zn lt 1 gt H lt 1 gt 3 34 r DM30 600 00 nf 226 6 56 9 66 n sFe wHOH Zn lt 2 gt Fe w 0 Zn lt 1 gt H lt 1 gt 2 72 r DM30 B B 11 26 n sFe s OH CK2 gt sFe sH0 Cd 1e H lt 1 gt 1 86 T B a Fig 13 Final Datensatz 14 po rre von 67 data selection ce e c e NN to Pol ho nico a a LJ gt 12 n3 e I na e mind Mf 22 s 3 co co e e n3 z eA EA EA ECA EA CA CA EA EA EIE ELE ca Dim 7 7 7 un inf in pr io LI LI n3 n3 Did 2 bn The data tables can also be formatted for a report or exported into MS Excel or pure ASCII format with the help of the buttons in the lower left corner of the form This of course will only work if some data records really have been selected through their checkboxes The output files will be placed in the directories specified under the entries ExcelPath or ASCIIPath respectively of the Local Options Furthermore it is re quire
28. parameter is a severe weakness of the Kg principle Such distribution coefficients tend to have large uncer tainties especially when inter or extrapolation to other system conditions is required They do neglect the underlying chemical reaction mechanisms between solids and the aqueous phase and thus can not reflect changes in chemical environment Moreover it is extremely time consuming to determine Ka values for the multidimensional parameter space usually to be considered in long term risk assessment predictions To overcome these problems strategies are required to unfold the Kg approach into more fundamental processes Such an approach will transform the single distribution coefficient into a vector of parameters such as E pH concentrations of various com ponents binding site densities surface areas and temperature The unfolding of Kj values leads to modern concepts that treat surface reactions as complex formations analogous to such reactions in homogeneous aqueous solutions Therefore these models are called Surface Complexation Models SCM SCM are site independent account for large variations in geochemical conditions and the acquisition of parame ters is comparatively cheap This should make it possible to perform more detailed sensitivity analysis to find the critical parameters to reduce the parameter space and finally to pave the way for more reliable models for contaminant transport I 7 1 2 Need for Sorptio
29. references can be traced back From there other parame ter sets stemming from the same source can be viewed e Each data record has a time stamp and editing remarks Therefore it is easy to reconstruct past data set assemblages at any later time or to check alternative data sets for a sorption modeling scenario e The user is supplied with an integrated online help in addition to an exhaustive printed documentation manual I 25 3 4 Integrated Tools The following tools as part of RES T simplify a comparison and uniform processing of the stored data e Automatic conversion of surface site densities in one unit sites nm e Normalization of pK and logK values to a reference surface site density of 12 05 sites nm Kulik 2002 e Automatic proposal of a chemical reaction equation for the surface complex formation after input of the stoichiometric coefficients e Statistical Data Evaluation opecific surface distributions referring to minerals Protolysis data distributions referring to minerals LogK distributions referring to ligand SCM models minerals and min eral groups Publication statistics referring to journals and year e Reformatting of bibliographic references according to editorial guidelines of dif ferent journals I 26 4 Database Content 4 1 Publications About 1400 literature references are already stored in the RES T database There the majority of information is published in journals whereof the J
30. result view forms described later There the small buttons labeled with D on the right hand side of various result fields including the query string repeated on top of the result form will open a form providing extra information II 16 4 1 Data for a selected mineral As compulsory first step a mineral from a scroll list must be selected If this is done some of the buttons below will turn from light gray into dark gray indicating that they are now in operation As long as no valid mineral is selected all buttons are inactive Keep in mind that some minerals are quite close to each other in their surface complexation behavior so if you do not find appropriate data for e g quartz you can also look under amorphous silica If the database does not contain data satisfying the query criteria an appropriate information box will pop up In case one wants to get the data not only for one mineral and or one ligand it is ad vised to use the query forms presented under Data Assembly amp Formatting 4 1 1 Specific Surface Area Pressing the button Specific Surface Area will list all data records containing specific surface areas for the selected mineral The columns are from left to right Specific Surface Area in m g Reported Grain Size in um and Literature Reference sorted by the area size and the literature reference code In Fig 3 you can see the query results for an example the specific surface area of
31. stants too In contrast other methods such as mean best estimate or batch sorption experiments are negligible About half of the surface complexation constants gathered in RES T are obtained by batch sorption experiments Other often used methods are the potentiometric titration method the measurement down of sorption isotherms or empirical correlations Graphical methods e g the double extrapolation technique were the most often used data processing procedures for the determination of protoly sis constants and surface complexation constants in the past For the last twenty years special software has been used chiefly This software contains routines for iterative im provement of the fit parameter and for automatic identification of compliance of conver gence criteria Especially the fit program FITEQL Westall 1982 Herbelin and Westall 1996 is applied Other programs such as GRFIT Ludwig 1996 GEMS Selector Karpov et al 1997 and C Letagrop Osthols 1994 are rarely used The second not so often used mainstream is the interconnection of speciation programs with imple mentation of several SCM with external parameter optimization Speciation programs with the ability of SCM involvement are MINTEQ MINTEQA2 Felmy et al 1984 Alli son et al 1991 MINEQL Westall et al 1976 with successors HYDRAQL Papelis et al 1988 and MICROQL Westall 1979a and b GEOSURF Sahai and Sverjenski 1998 CHESS van der Lee 2003 HARPHR
32. this field showing a clock will set the modification stamp of that record to the current time and user 6 1 Publication This input form organizes the storage of any bibliographic information relevant for the RES T database Depending on the selection made in the field Type certain input fields may be shown or not thus limiting the available fields see below for a complete list to the necessary ones Fig 15 shows the form layout for the publication type Arti 3 cle Author s Eg TE Davis JA Lumpkin GR Chisar A and Waite TD Tithe il complexation model of uranyl sorption on Georgia kaolinite Year 2004 Mnemonic Code PDLCwD4 Pages 151 162 Type Article gt Access Copy Journal Appl Clay Sci Yolume 26 Comment Internal Status Pure Listing r Last Modification at 09 08 2004 15 42 00 by anke Fig 15 Input and editing form for p publication data El a uuu i here article in a Datensatz 14 4 1457 F r e vor 1461 journal The Memo button in the footer section of this form converts the bibliographic refer ence into formats according to editorial guidelines of different journals The formatted reference is shown in a separate window already marked and highlighted ready for 11 28 Cut amp Paste into other documents The desired journal style can be selected through the Administration menu see there for details Author s
33. von 42 taeritert formation Mineral Select from a scroll list if not available go back to the input mask Mineral and add the respective mineral See there for further details Original Publication Select from a scroll list if not available go back to the input mask Publication and add the respective paper See there for further details Citation in f information is only cited in a secondary data reference add this citing paper If later access to the original reference is available clear the citation entry and move the information about citation s into the comment field SCM Type Select from a scroll list if not available go back to Advanced Editing and add the respective model under Surface Complexation Model See there for details Site Protolysis Reference Reference to the used site protolysis data maybe the same work or citation from another publication select from a scroll list presenting the publication reference code the SCM type acronym being identical to the above se lected SCM type and the PID unique protolysis data record identifier The latter is important when a publication contains more than one different protolysis data sets for a given combination of mineral and SCM type Ligands Selection of a major 1 required and secondary 2 for ternary surface complexes optional ligand forming the surface complex In case of ternary complexes the metal should always become the 1
34. way for this charge effect additional terms have been introduced into adsorption models modifying the activity of sorbate ions These terms describe the electrical work neces sary to penetrate the zone of electrostatic potentials resulting in a difference between the activity of ions M with the charge z near the surface and the same ions M in the bulk solution 9 M m je mp where the second term of the right side the Boltzmann factor is defined by the Fara day constant F the ideal gas constant R the absolute temperature T and the electric potential Y near the surface The activity of surface species is set to one by definition Another essential assumption is the diprotic acid model used to describe the protona tion and deprotonation of surface sites 2 pK approach XOH XOH H 10 XOH XO H During some surface complexation experiments it turned out that the observations could only be explained satisfactory when assuming two site categories on one sur face having different binding properties strong and weak binding sites with differing surface site densities The strong binding surface sites are considered to be acidic with a large degree of polarization Weak binding sites are basic sites with a much lesser degree of polarization very similar to anion exchange sites This concept is applied mostly to cation sorption for anions no significant difference in sorbing on strong and weak site
35. C Model are the most often utilized combina tions with the 1 pK Model CD MUSIC Model The MUSIC Multisite Complexation Hiemstra et al 1989 and its extension CD MUSIC Charge Distribution Multisite Complexation Model Hiemstra and Van Riems dijk 1996 have been developed to consider the dissimilitude of surface sites and crys tal surfaces This approach enables a more realistic description of surface species and binding mechanisms than the conventional surface complexation models but demands a detailed knowledge of morphology and crystal structure of the particle surface char acter and distribution of the binding sites Three differently coordinated surface sites are assumed which are in the deprotonated state are X 0 X O und X3 0 Therefore only two forms can generate charged sites X OH und X40 7 2 3 6 Non Electrostatic Surface Complexation Model Unlike other SCM the Non Electrostatic Model Kurbatov et a 1951 Bradbury and Baeyens 1997 assumes that electrical charge at mineral surfaces does not effect the surface complexation Thus the activity of a surface species is equal to its concentra tion An apparent equilibrium constant is calculated Although this model oversimplifies surface complexation several investigators have used this approach to describe sorption One of the reasons may be that the Non Electrostatic Model requires the fewest fitting parameters The description of acid
36. Cu lt 2 gt Fe singly OH Cu lt 1 5 gt log K Reaction constant for the surface complex formation If published the un certainty of log K can also be included Fit Method Method software used to derive SCM parameters from the sorption ex periment Select from a scroll list If a method is not available go directly to the table Fitting there is no extra input mask available and add the respective method Experiment Original data source for the derivation of surface complex formation con stants This is not necessarily an experimental technique but could also be just taken from the literature single reference or weighted average or be computed based on crystallographic data or other theoretical considerations Select from a scroll list if not available go back to Advanced Editing and add the respective method under Ex perimental Method See there for details lonic Strength of lonic strength of the background electrolyte in mol L If experi ments for various ionic strengths are reported specify the lowest one in this field and mention the other ones in the comment field If the reported protolysis constants refer to an extrapolated infinite dilution leave the field blank and specify all experimental II 38 ionic strengths in the comment field If there are mixed background electrolytes or ex periments with different electrolytes specify them in the comment field The type of the background e
37. Eng Massachusetts Inst Technol Cambridge MA e Wilhelm R G and Beam P eds 1999 Understanding variation in partition coefficient Ky values EPA Report 402 R 99 004A Washington e Yates D E Levine S und Healy T W 1974 Site binding model of the electrical double layer at the oxide water interface Journal of the Chemical Society Faraday Transactions l 70 1807 1818 I 45 Development of a Mineral Specific Sorption Database for Surface Complexation Modeling Entwicklung einer mineralspezifischen Sorptions Datenbank f r Oberfl chenkomplexierungsmodelle Project PtWt E 02E9471 Part Il Manual RES T Rossendorf Expert System for Surface and Sorption Thermodynamics 1 Release Vinzenz Brendler Anke Richter Dresden September 2004 Disclaimer You expressly acknowledge and agree that the use of the RES T database including the database management system and all data records the SOFTWARE is at your sole risk The SOFTWARE and technical support if any is provided as is and with out any warranty of any kind express or implied To the maximum extent permitted un der applicable laws FZ Rossendorf expressly disclaim all warranties express or im plied including but not limited to implied warranties of merchantability fitness for a par ticular purpose and non infringement FZ Rossendorf does not warrant that the func tions contained in the SOFTWARE will meet your requirements or that th
38. FZR 409 FZR 409 September 2004 ISSN 1437 322X Wissenschaftlich Technische Berichte Vinzenz Brendler Anke Richter Cordula Nebelung Annett Vahle Development of a Mineral Specific Sorption Database for Surface Complexation Modeling Entwicklung einer mineralspezifischen Sorptions Datenbank f r Oberfl chenkomplexierungsmodelle F rderprojekt PtWit E 02E9471 Part I Final Report Part Il Manual FZR Forschungszentrum Rossendorf Wissenschaftlich Technische Berichte FZR 409 September 2004 Vinzenz Brendler Anke Richter Cordula Nebelung Annett Vahle Development of a Mineral Specific Sorption Database for Surface Complexation Modeling Entwicklung einer mineralspezifischen Sorptions Datenbank f r Oberfl chenkomplexierungsmodelle F rderprojekt PtWt E 02E9471 Part I Final Report Part Il Manual thek FZ Rossendorf u JUN ZR Forschungszentrum Rossendorf Development of a Mineral Specific Sorption Database for Surface Complexation Modeling Entwicklung einer mineralspezifischen Sorptions Datenbank f r Oberfl chenkomplexierungsmodelle Project PtWt E 02E9471 Part I Final Report Vinzenz Brendler Anke Richter Cordula Nebelung Annett Vahle Dresden September 2004 Abstract An MS Access based digital thermodynamic sorption database has been developed and tested This database is named RES T Rossendorf Expert System for Surface and Sorption Thermodynamics lt is
39. L and Excel must be absolute ones including the hard disk drive letter II 49 8 General Help Pressing the button Help will open the start page of an HTML based RES T manual provided a web browser is already installed on the PC Inside the manual one can navi gate in the usual manner with all the menu screenshots providing click sensitive areas In addition to this general help most of the important menu forms also provide a help button in their footer section which will bring the user to a section of the online manual relevant for the respective menu form The online manual essentially provides the same information as can be found in this document 9 Acknowledgement Financial support from the German Federal Ministry for Economics and Labor BMWA under contract No PtWt E 02E9471 is gratefully acknowledged The RES T team Vinzenz Brendler Anke Richter Cordula Nebelung Annett Vahle would like to thank Martin Ebschner Jens Mibus Thuro Arnold Sindy Gr ger and Ber tram Skibinski for their valuable contributions Finally the steady support by the director of the Institute of radiochemistry Prof Gert Bernhard and his predecessor Prof Thomas Fangh nel is very much appreciated 10 Contact Dr Vinzenz Brendler Forschungszentrum Rossendorf e V Institute of Radiochemistry P O Box 51 01 19 D 01314 Dresden GERMANY 49 351 260 24 30 Phone 49 351 260 35 53 Fax res3t fz rossendorf de http www f
40. Layer Model see Fig 4 furthermore it considers the sorption of background electrolyte ions The Basic Stern Model also takes account of the fact that both the surfaces and adsorbing species are charged and that the surfaces change their charge when ionic sorption takes place The solid solution interface comprises of an empty Stern layer and a flat diffuse double layer The correlation between surface charge o and surface potential y can be described similar to the Triple Layer Model but with only one capacity O 0 0 0 15 o C CF V Y Y The surface functional group is defined by HO X OH2 This convention allows only one protonation or dissociation to occur for every two surface hydroxyl groups y Basic Stern Model Ya Diffuse Layer 0 X4 Xq Oo O4 Og Fig 4 Positioning of ions and correlation between charge and potential for the Basic Stern Model I 19 1 pK Model Other than the generic 2 pK formalism the 1 pK approach Bolt and van Riemsdijk 1982 Hiemstra et al 1987 describes the charge of the surface by an assumption of only one equation Ebr Oo gt 16 XOH 4H XOH K 10 and replaces so the protolysis equations in chapter 2 3 1 Up to now this approach is not so widely used yet The Constant Capacitance Model the Diffuse Double Layer Model and the Triple Layer Model all in principle can be combined with this approach but the Stern Model and the CD MUSI
41. M It assists the identification of critical data gaps the evaluation of existing parameter sets consistency tests and the establishment of selected reference data sets As to the knowledge of the authors so far there is no such digital thermodynamic database for surface complexation equilibria existent world wide despite the vast amount of available data The RES T database is intended for an international use This requires high standards in availability consistency and actuality Therefore the authors of the database decided to couple the database onto an authorization tool 11 7 This decision led to a categorizing of users into at the moment three groups e users that want to exploit the database for their needs by searching for data re cords or assembling their problem specific data set for more complex systems The members of that group which is the default group are only allowed to view extract and process data for output but neither to change the database content nor its internal structure e editors that are considered qualified for the assessment of publications focused on surface complexation and related areas In addition to the actions allowed for mere users they can add and edit most of the database records e administrators with unrestricted access to the underlying database engine They are allowed to modify table structures and internal relationships input and output masks and subroutines etc They should mainta
42. Q Brown et al 1988 or PHREEQC Parkhurst 1995 Parkhurst and Appelo 1999 I 36 6 2 Application In various papers and lectures the REST project team presented application examples for the RES T database Namely the database helped to illustrate the current blind predictive capabilities of SCM see the chapter Publications below for a respective bibliography This will promote a more widespread use of modern sorption concepts such as surface complexation combined with surface precipitation ion exchange and the formation of solid solutions The systems covered in these papers are Np V sorp tion onto hematite U VI sorption onto quartz Se sorption onto goethite and Cu ll sorption onto goethite Together with the database a strategy was derived to obtain reliable and comprehen sive sets of sorption data for complex natural systems This includes approximation methods to fill crucial data gaps Based on the information about the minerals collected in the sorption database RES T first a set of relevant surface species must be formed Then respective surface complexation parameters are taken from RES T the binding site density for the minerals the surface protolysis constants and the stability con stants for all relevant surface complexes To be able to compare and average thermo dynamic constants originating from different sources a normalization concept is ap plied A general aim is to keep the number of parameters at a mini
43. SF0 0 5H2NO3 0 40 0 82 rfkozb unzc2e r z3r0 05H 102245 gt 5i20 002 2 H lt 1 gt 750 732 r jko2b A UD2 lt 2 gt 550 05 AJ 00220 2H20 52 0 0020M 2 lt 2 gt 4 He 17 80 18 22 P KU2b UO2 lt 2 Pp faeS 0 0 5 Hj U02 lt 2 gt H2C03 2H20 512 0 102 0H 2 Cr 24 90 25 32 T KOZE T JUO2 lt 2 r 2 5H0 0 5 4 2002 lt 24 gt H20 512 0 4U02 2 04 3H lt 1 10 10 1052 r Kn26 m HT 5 0 0 5 H 0022 H20 512 0 102 04 lt 1 gt 3 HcT 12 24 12 64 rfko2b T NpD02cle r s5H0H Np02 lt 1 gt S O NpO2 H lt 1 gt 65 DES Naste r sSHOH Nact 5i 0 Na Hels 0ra 10r KvrMN88 r sde rf st0H Cie 388068 Hc 257 r krMNS6 r Fig 5 Query results Made r s5HD0H Nacl gt Si0 Na Holes 0 85 r ofsurface Se complexation data for an Quartz with Triple Layer Model Datensatz lad 1 for s on 67 y Surface Complex Formation for a selected ligand The respective button is only activated when both a valid mineral and a valid ligand is selected It lists all data records containing surface complex formation constants for the selected combination of ligand and mineral The columns are from left to right SCM Type Chemical Equation log K Exp Norm and Literature Reference see Fig 6 sorted by SCM type and literature reference code II 19 REST List of Surface Complexation Data for Quartz El w
44. Sand ant Sample Mame Min u Sil 5 Preparation prepared from natural quartz sand from Berkeley Springs pretreatment leaching and washing acid Form Specific Surface rea Primary Sample Origin rea Size 415 in m q Experiment B E T s Grain Size 25 mn um Comment particle size average diameter citation in 559 a length Eo width ratio 4 9 electron photomicroscopy elongated irregularly shaped particles of 1 10pm in length NZ BET pr Internal Status Details Last Modification at 13 10 2003 11 24 4 by anke i Fig 17 Input and amp lad bs Bi editing form for sample specific data Datensatz 14 1 56 r r l on 650 p Mineral Select from a scroll list If not available go back to the input mask Mineral and add the respective mineral See there for further details Original Publication Select from a scroll list if not available go back to the input mask Publication and add the respective paper See there for further details Citation in f information is only cited in a secondary data reference add this citing paper If later access to the original reference is available clear the citation entry and move the information about citation s into the comment field 11 32 Primary Sample Origin Origin of the mineral phase commercial synthetic or natural product Supplier Manufacturer of a commercial product or depository for a natural product Select
45. Thus it is a logical conclusion that the creation of such a thermodynamic sorption data base is an urgent need being easy to use and comprehensive 1 3 Goals The major goal of the project is the design and implementation of a digitized version of a thermodynamic sorption database It should provide a sound foundation for the use of SCM in risk assessment studies and finally be able to deliver recommended data sets for such SCM applications The utilization of thermodynamically consistent data sets is indispensable for a correct modeling of surface complexation This means that the data sets for the sorption of all relevant ligands on a mineral must be based on identical fundamentals e Use the same specific surface area e Assume the same type and number of binding sites e Use the same thermodynamic model SCM e Use the same protolysis constants e Use the same capacities if required by the SCM otrictly speaking further qualifications must be fulfilled e Same speciation in aqueous solution for all sorption constants e Known ionic strength and possibility to extrapolate or interpolate to the model ionic strength The above mentioned demands on data consistency are realizable only in rare ideal cases To allow for an at least partial data consistency during the compilation of data sets for special modeling problems internal references of the underlying specific sur face areas binding sites and protolysis constants must be pr
46. View 32 Data Assembly and Formatting e eere eere eene eee e eerte reete eee e sean 32 Data Input and Editi iioii ei eoe ie iiie iaaea eeepc et retener ees 33 A e A 33 General Help 2 EEG 34 SUMMAR Vcc 35 A AA 35 APDICat on neuere 37 Bement and Uflat zu 38 Outlook a 38 Publica ION cti 39 ACKNOWLEDGEMENT nenne 41 REFERENCES sn 42 List of Figures Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig Fig 11 12 Positioning of ions and correlation between charge and potential for the Constant Capacitance Model cccccceeee cece eeeeeeeeeeeeneeeeeeeesaaees Positioning of ions and correlation between charge and potential for the Diffuse Double Layer Model sesssesessse e Positioning of ions and correlation between charge and potential for the InpleiEayer Model RE Positioning of ions and correlation between charge and potential for the Basic Stern Model adan aida Internal relationships and content of the data tables of RESTT Major journals publishing SCM papers esee Distribution of specific surface area data records Distribution of protolysis data records referring to minerals Distribution of surface complexation constants records referring to TINCT CREE TU UIT Distribution of surface complexation constants records re
47. a Evaluation Set Reference Format set Manual Path Export to MySQL Reload Local Options Fig 25 Administration menu of the RES T database 7 1 Daily Backup Pressing this button starts a backup of all database tables into a new MS Access data base Its name follows the pattern RESST YYMMDD mdb where YYMMDD stands for digits representing year month and day of the backup and stands for the current user name The backup is placed in a directory specified by the Local Op tion setting BackupPath This button is not activated for users without administrative privileges 7 2 Statistical Data Evaluation This opens another menu with various options to perform a statistical data evaluation and to export the results into MS Excel spreadsheets to e g create graphs or do more elaborate data processing These spreadsheets will be placed in the directory specified under the entry ExcelPath of the Local Options II 46 Specific Surface Distribution Creates a table giving the number of SSA records per mineral and puts the results into a spreadsheet named SSA minerals xls Protolysis Data Distribution Creates a table giving the number of surface site pro tolysis records per mineral and puts the results into a spreadsheet named pk mineral xls log K Distribution Creates tables giving the number of surface complexation con stants per SCM type per ligand per mineral and per mineral group The results ar
48. al if it is still missing Then comes the input of specific surface area values which in turn is a prerequisite for records containing site densities and surface protolysis constants Finally surface complexation data can be edited This order is also reflected by the layout of the Data Input amp Editing menu form as shown in Fig 14 When an input field has a pale yellow background color this indicates that an entry into this field is compulsory Leaving such fields empty is not possible the database will not allow to store such incomplete data records A remark to bibliographic references required by nearly all input forms A selection as Original Publication always means really the work where the data record has been published first If the information can only be derived from a secondary reference then the latter must be specified in Citation in When later the original reference becomes available the citation entry can be removed or moved to the comments II 27 The following book keeping information apply to all forms being part of the input inter face They may be deleted hidden for external users in later revisions e Internal Status This field gives information about the internal processing status of a given data record e Last Modification These fields specify the time and date of the last modification of the given data record and who of the registered users did it Pressing the small button on the right of
49. and Advances in Nuclear and Radiochemistry Extended Abstracts of papers presented at the Sixth International Conference on Nuclear and Radiochemistry NRC 6 29 Au gust to 3 September 2004 Aachen Germany S M Qaim and H H Coenen Ed Schriften des Forschungszentrums J lich Reihe Allgemeines und Interdisziplin res Band 3 2004 l 40 7 Acknowledgement Financial support from the German Federal Ministry for Economics and Labor BMWA under contract No PtWt E 02E9471 is gratefully acknowledged The RES T team Vinzenz Brendler Anke Richter Cordula Nebelung Annett Vahle would like to thank Martin Ebschner Jens Mibus Thuro Arnold Sindy Gr ger and Ber tram Skibinski for their valuable contributions Finally the steady support by the director of the Institute of radiochemistry Prof Gert Bernhard and his predecessor Prof Thomas Fangh nel is very much appreciated 41 8 References Allison J D Brown D S und Novo Gradac K J 1991 MINTEQA2 PRODEFAZ2 a geochemical assessment model for environmental systems Version 3 0 user s man ual Report EPA 600 3 91 021 U S Environmental Protection Agency Environ mental Research Laboratory 106 p Arnold T Zorn T Zanker H Bernhard G and Nitsche H 2001 Sorption be havior of U VI on phyllite experiments and modeling Journal of Contaminant Hy drology 47 219 231 Bennett D G Liew S K Mawbey C S und Read D 1992 CHEMTARD theore
50. and an organic reaction partner become the 11 37 2 ligand If the required ligand is not available yet go back to Advanced Editing and add the respective ligand under Ligands See there for details Site Type Select from a scroll list If a surface site type is not available yet for a certain mineral one has to go to the Advanced Editing menu and assign this site type under eurface Site Types to the respective mineral See there for details Generic site types should only be used when it is not clear which site type is meant by the authors Coefficients Specification of the stoichiometric coefficients for all components forming the surface complex For reaction products give negative numbers Equation Equation of the chemical reaction forming the surface complex The unre acted surface site always occurs on the left hand side Proposal for Equation The button will provide a proposal for the surface complex formation generated by the database It can be accepted the proposal will then auto matically be inserted in the equation field or rejected To illustrate the notation recom mended for chemical equations some examples are given below In case of ternary complexes the metal should always be written in front of an additional organic ligand Examples AI OH Ga lt 3 gt H2O Al O Ga OH lt 1 gt 2 H lt 1 gt 2 Fe s OH UO2 lt 2 gt Fe s O 2 UO2 2 H lt 1 gt Fe singly OH 0 5
51. blications citing that work short summaries about content Here it should also be noted if the paper actually contains no extractable information about SCM could be the case in review articles or works covering theoreti cal aspects model comparisons or structural investigations 6 2 Mineral This form Fig 16 is used to edit all information required to characterize the minerals oee also under the chapter Content Policy for the definitions of a mineral phase II 30 Official English Name Buarz Alternative Trivial Name Formula 5i02 Mineral Group quartz varieties r Mineral Series rock forming minerals 1 r Molar Mass 60 084 in q 7 mol Density 65 ing 7 co Add Edit Reactions Mineral Alteration Thermodynamics amp Kinetics Product Reference Chemical Reaction Datensatz 14 4 Comment hd 2 Fig 16 Input and editing Datensatz ala 5 rt rse von 111 form for mineral data Official English Name Correct mineralogical name of the mineral Alternative Trivial Name Trivial commercial name of the mineral in English Formula Chemical formula of the mineral There are only few examples of minerals with alternative chemical formulae namely ferrihydrite The pragmatic approach used here is to specify just one formula and recalculate accordingly all values based on the alternative formulae which then of course must be mentioned in the comment field This affects only site de
52. constants are gathered in the database These records are associated to the minerals as shown in the following fig ure RES T database Distribution of log K data records Others Corundum Quartz Goethite Montmorillonite x Anatase Magnetite Rutile A Kaolinite Vernadite Fig 9 Distribution of amorphous Ferrihydrite surface complexation Silica Alumina constants records Haematite referring to minerals When converting this figure into a distribution with respect to the major mineral groups the picture looks like in Fig 10 Obviously most of the sorption experiments so far con centrated on those minerals that are easy to handle in the laboratory and have well defined surfaces Whereas some of them have considerable practical relevance others are merely model systems Especially the important groups of manganese minerals mica and feldspars are underrepresented so far I 29 RES T database Distribution of log K data records Aloxides Ti oxides Mn oxides hydroxides hydroxides E Carbonates Quartz varieties Fig 10 Distribution of Clay surface complexation minerals constants records referring to mineral groups Fe oxides hydroxides In Fig 11 you can see the distribution of log K data records referring to the major ligands contaminants and matrix ions RES T database Distribution of log K data records Fig 11 Distribution of surface complexation constants records
53. d scroll lists a quick tip about the pur pose of that very element will pop up e By using the TAB key it is possible to move inside forms from one button to the next and from one input field to the next e Pressing the ESC key cancels all changes done so far in a form as long as it has not been saved in the meantime explicitly or by switching to another re cord RES T Rossendorf Expert System for Surface and Sorption Thermodynamics Data Query amp View Data Assembly amp Formatting Data Input amp Editing Administration General Help This project is funded by the German Federal Ministry of Economics and Labour BMA under contract Mo Pete E 02E9471 which is gratefully acknowledged REST FZ Rossendorf 2007 2004 Version 1 54 Fig 1 Main menu of the RES T database Close Database amp Exit hie II 12 3 1 Content policy Both when entering or editing data records and when evaluating data query responses the user should keep in mind some general principles steering the selection input han dling and structuring of sorption data inside the RES T framework When is a data set considered a separate record At least one required pa rameter must be different from other data records or parameters from different other sources have been combined to a new record What is considered a mineral This is not so clear a look into http www webmineral com Mineral_Definition shtml gives various mineral def
54. d to give the correct path to a simple ASCII editor program under the entry Note pad also as part of the Local Options A good example for such an editor is the standard MS Windows notepad More about meaning and handling of Local Options can be found under the Administration menu 5 5 Speciation Code Here the user specifies the software geochemical speciation or reactive transport de fining the output format of the final data set and to be selected from a scroll list 5 6 Export it Pressing this button eventually triggers the export of the assembled data set into an ASCII file with the before defined format This feature is not implemented yet II 26 6 Data Input amp Editing To prevent unauthorized data manipulation and the emergence of different unsynchro nized database versions the whole editing shell can be uncoupled and hidden from the user This is the default for users not having administrative permissions RES T Data Input amp Editing Publication Mineral sample Specific Data Site Density amp Surface Protolysis Surface Complex Formation Advanced Editing Fig 14 Data Input amp Editing menu of the RES T database To ensure that all lists for input selections are properly set up during the data input pro cedure a certain input order should be followed starting with the input or update of bib liographic data if not already correctly present Next step would be to add the miner
55. del theory to be used in tables and scroll lists Major Reference s Important publications dealing with the SCM sub model theory i e development of the theory extensions major applications limitations etc The table shows the literature reference code authors and title of the publications Add Edit References The button will open an additional form Literature SCM The ory with the fields SCM Type which defaults to the SCM type specified in the calling form Reference where a publication reference code can be selected from a scroll list and Comment a place for any additional remarks Comment Additional remarks about theoretical aspects application limits required fit parameters resemblances with other models implicit assumptions about systems or parameters etc 6 6 2 Experimental Methods As for the SCM types above also this form see Fig 22 gives some short background information and essential references but here with regard to experimental methods relevant for sorption experiments in a wider sense Technique Potentiometric Titration Major Reference s Add Edit References ES KS350 Kummer R Stumm WW ae complexalion of organic acids on hydrous AZ C3 Datensatz 4 4 Used to Derive Specific Surface Protolysis log K Species Surface Site Density Constant Value Evidence Area L Iv Iv m a Comment often termed acid base titration Fig 22 Advanced Editing q s
56. distribution coefficient Ky The Kg concept is the one most often applied in geochemistry at present It is used in two different versions based on either of the following definitions a Conventional Ky model oXOH M K A M Here Ky represents the ratio of the specific concentration of the metal sorbed onto the surface given in mol g solid to the concentration of the dissolved metal sum over all aqueous species containing the metal given in mol L solution b Activity Kg model XOH Mj Mj Contrary to the above definition here the activity of the sorbed species and the free 2 Ki metal cation in solution is considered 2 2 2 Langmuir Adsorption Model The Langmuir adsorption Langmuir 1916 differs from the Kg approach only in that it requires specification of the total number of surface sites available It assumes a reac tion between a distinct surface site and the free metal cation giving an equilibrium con stant according to the equation ar _ WXOH M v AL M XOH This formulation is equal to the expression most often given as DXOH yu M 4 XOH M1 K Whether a description with the Langmuir isotherm is correct can easily be verified by plotting M XOH M using a linearized version of the defining equation l 12 M l M 5 y a m XOH M K XOH 7v XOH The introduction of total surface site densities certainly improves the so
57. e records actually should be included into the final data set Suspicious records can be rejected e g or in case of several competing values for the same surface reaction an appropriate choice can be made To assist these decisions the small buttons on the right hand side of the data fields labeled with D give access to a more detailed view of the data record similar to the query result forms There are two buttons below the table that either select all checkbox button or none rubber button entries II 25 SCM Type DDL D pK and log K values are all normalized to the reference state Mineral Area in Sites pK_1 pK_2 Chemical logK Literature m g nm Equation Reference Goethite nf 7940n 325 n sFe DH Cu lt 2 gt Fe 0 Cucle H lt 1 gt 1 28 r AD35c 140 6 79 9 25 n Fe DH Cu lt 2 gt 504 lt 2 gt Fe 0H Cu504 8 75 p ADS5c 228 6 56 9 66 n sFelw DH Pb lt 2 gt Felw 0 Pb lt 1 gt H lt 1 gt 0 50 r APGv94 28 6 56 9 66 n Fe wHOH Cd lt 2 gt Fe w 0 Cd lt 1 gt H lt 1 gt 2 55 r APGv34 26 6 561 9 66 nf gt Fe w 0H Co lt 2 gt Felw 0 Co lt 1 gt H lt 1 gt 3 81 r APGv34 18 11 22 n sFe DH Cuc2 gt sFe 0 Cucle H lt 14 gt 2 21 T 18 11 22 n sFe DH Cd lt 2 gt Fe 0 Cd lt 1 gt H lt 1 gt 0 90 F BHXB502 18 11 22 n sFe OH Ni lt 2 gt Fe 0 Nic1 gt H lt 1 gt 45 28 r BHXBS02 B 11 26 n sFe sKOH Ni lt 2 gt Fe s O Ni lt 1 gt H lt 1 gt 1 46 r BKEC94 600 00
58. e nennen nnn nnn 12 3 1 Content pol d 13 E Navigation DUCLODS E 14 4 DATA QUERY amp VIEW een ern popa ctos gos 2e aces 16 4 1 Data for a selected nilneral eei eeeo eee eene eee ease eso vov esa aerae aaa ee ea noss ioios 17 4 1 1 pecto SUN aCe ATCA ee ee 17 4 1 2 Site Density Pro B SIS u a 17 4 1 3 Surface Complex Formation ee Bea 19 4 2 Publications sisi REA 21 5 DATA ASSEMBLY 8 FORMATTING eere nun nun nenn 22 5 1 Mineral Set eris M 23 5 2 Lican d Set CSI 23 5 3 Inspection SCM Choice senssa i eoe ee reprae eoe nee odes o aeo rede to edo ee eue tee 24 5 4 Final Data Selecione 25 5 5 SPEEIAUON C Ode een iM 26 5 6 DN AP O 26 6 DATAINPUT amp EDITING diee ee ida 27 6 1 PUDICACION rondan R 28 6 2 A 30 6 3 sample Specific DACA e der E ese een 32 6 4 Site Density amp Surface Protolysis eee eere e eee ee eee eee eerte eene 33 II 3 6 5 Surface Complex Formation 36 60 Advanced um 39 6 6 1 SCHI Ti O m MM are Ser 40 6 6 2 Experimental Methods aii 41 6 6 3 Species SPECIHOSCHODIE BVIGGPIOS aa 42 6 6 4 Lie NE DoDo eron 43 6 6 5 SMa o Pes eer tater Me Te eee 44 6 6 6 Mineral Alteration and Kinetics ccocccooononccnnnnnnnnnnnnccnnnnnnnnnnonanoccnnnnnnnnnnnnns 45 T ADMINISTRATION teense aie nine nan 46 7 1 Daily Backup une li ea 46 7
59. e operation of the SOFTWARE will be uninterrupted or error free or that defects in the SOFTWARE will be corrected Furthermore FZ Rossendorf does not warrant or make any represen tations regarding the use or the results of the use of the SOFTWARE in terms of its correctness accuracy reliability or otherwise No oral or written information or advice given by FZ Rossendorf or its authorized representatives shall create a warranty or in any way increase the scope of this warranty Some jurisdictions do not allow the exclu sion of implied warranties so the above exclusion may not apply or may be limited FZ Rossendorf retains all right title and interest in and to the SOFTWARE and any rights not expressly granted to you herein are reserved by FZ Rossendorf Any attempt to transfer any of the rights duties or obligations hereunder is void You may not rent lease or loan the SOFTWARE You may not reproduce distribute publicly perform publicly display modify or create derivative works of or based on the SOFTWARE Copyright O 2001 2004 by FZ Rossendorf e V All rights reserved II 2 CONTENT T INTRODUCTION 2 2 2 2 nos 7 2 INSTALLATION esse en 9 2 1 RES T Software Packase iiie etie iei ea 9 2 2 Minimal System Requirements eee eee e eee eee e eee eee ee eene eee s oett teet eese suas 9 2 3 Program Setup zuo dh iier Een oo hodie 10 3 START MENU MAIN MENU eeeeree een
60. e put into spreadsheets named logK SCM xls logK ligand xls logK mineral xls and logK group xls respectively Publication Statistics Creates tables giving the number of publications per year and per journal The results are put into spreadsheets named publ year xls and publ journal xls respectively 7 3 Set Reference Format Here you can preset the output format of the Memo field in the publication input and editing form Citation formats required by the editorial guidelines of the following jour nals can be selected e Geochimica et Cosmochimica Acta Clays and Clay Minerals Applied Geo chemistry Default e Journal of Colloid and Interface Science e Environmental Science amp Technology Langmuir e Soil Science Society of America Journal e Colloids and Surfaces e Radiochimica Acta e Journal of Contaminant Hydrology However it must be pointed out that the notation of the authors names is not correct Also italic and bold formats are not included 7 4 Set Manual Path Here the database administrator can specify whether the HTML based online help should be accessed through the Internet or from a local file directory This button is not activated for users without administrative privileges The path required for Internet ac II 47 cess is predefined in the table Administration as entry RES3T URL and must be a valid URL address The local file directory can be set in the local optio
61. ecords an SCM sub model must be selected to enforce at least a minimum degree of internal data consistency and the data set can then be further refined The definition and selection of the data collection must exactly follow the given order As long as a previous step is not accomplished all further buttons are inactive indicated by a light gray color of the respective buttons see Fig 9 The final data set can be exported in a file to be used in other geochemical speciation codes such as MINTEQA2 Allison et al 1991 GEMS Karpov et al 1997 PHREEQC 2 Parkhurst and Appelo 1999 or HARPHRQ Brown et al 1988 and reactive transport software such as CHEMTARD Bennet et al 1992 or OS3D GIMRT Steefel and Yabusaki 1995 In case of such data exports the output format will automatically be adapted to the specific requirements of the different software pack ages This feature however is not implemented yet Instead output into a general ASCII format is provided which can easily be transformed in the required speciation input format 1 Mineral Set Assembly 2 Ligand Set Assembly 3 Inspection SCM Choice 4 Final Data Selection Speciation Code 6 Export it Fig 9 Data Assembly amp Formatting menu of the RES T database M M M EA uj 11 22 5 1 Mineral Set Assembly An alphabetically sorted list of all minerals is presented where the user can make mul tiple selections through the check boxes on t
62. ection of Ligands FE arbx lt 1 gt yo Er Dee ajaja T mk 212123 12 Ta j Ej E m 1 T Fa I we Bo BO NENNEN Bo gt gt C IO Es NEN ES S C NENNEN Es NENNEN EE BO BO BO BEL c IE BO Bo E oom ES Datensatz lal 113 npe Fig 11 Selection of ligands 5 3 Inspection SCM Choice This form lists all relevant data records based on the user selections for minerals and ligands The first column on the left specifies the applied SCM sub model then the mineral follows For each surface complex formation data record also the associated experimental specific surface area and site densities are given Then three columns fol low given the protolysis constants and the complex formation constant all normalized to the standard site density of 12 05 nm The next fields give the chemical reaction and the literature reference The results are sorted by SCM type literature reference code and mineral name see Fig 12 At the bottom of the form the button showing two tables will open a cross table giving the number of data records per combination of mineral and ligand Finally the user then has to decide which SCM sub model the assembled data set should be based on This may of course drastically reduce the number of data records but is a requirement for an internally consistent data collection The SCM is to be se lected from the scroll list at the bottom of the form then the Back
63. ed mineral covering all ligands The columns are from left to right SCM Type 1st Ligand Chemical Equation log K Exp Norm and Literature Reference see Fig 7 sorted by SCM type ligand formula and literature reference code RES T List of Surface Complexation Data for Quartz E SCH 1st Chemical Literature Type Ligand Equation 3 Reference MIDDL CUDZ 2 Dje 35 04 U02 lt 2 gt 502 002 2 H lt 1 gt pp rjJuna2e r 2 5HD0H U02 lt 2 gt sSi 0J2002 2H lt 1 gt ppL r Ba2e r s5r0H Bae2e sSED Bacle H lt 1 gt DDL r Sk2e r s5r0H 5m2e s5r0 Srcle Hel gt 1 23 DDL r Ex 3e r s5r0H Eus3 gt sSrD Euc2e H lt 14 gt DDL r amp mci3e r 5rD0H Ame3 gt 5i D Ami2 gt Hel gt Jun ppL r uDac2e r s5r0H U02c24 gt s5r0 0261 e H21 gt 0 30 ppL rJuoa2e rf gt siOH U02 lt 2 3H20 s5E0 UO2 12 4 ppL r u zs2e r s5rO0H 1102 lt 2 gt s5iO UD2 01e H21 gt Fi O bo rJuozx2e Ir sSioH U02 lt 2 gt H20 Si 0 UO2 0H 2H amp 3 r PTBP38 on 25 0H 3 U02 lt 2 gt 5H20 sSiO UO2 3IDH 17 47 PIPTEPIS mj ppL r Nale r s5r0H Macle Si O Na H21 gt E r Tz02 ml poi Pee EST SHO PuOHK2 gt 2 421 493 r waTOIb n en em on ha oo on j anj ee a La a JPITPO ri 0 42 r JPTBP38 co e 1342 T je na ca En c e c cn am pals Ee Pal ra DP uad
64. es can not be assigned to one of them If there are mixed back ground electrolytes or experiments with different electrolytes specify them in the comment field The type of the background electrolyte medium salt can be selected from a scroll list If not available go back to the table Electrolyte there is no extra input mask available and add the respective medium So far there is no commonly agreed upon model for activity coefficients for surface species rendering an extrapolation of reaction constants from the experimental ionic strength to infinite dilution a very difficult task 3 2 Navigation buttons Various navigation elements buttons may occur on the footer section of database forms Clicking them will start actions as described below II 14 Table 1 Navigation buttons Du This button will Open a context sensitive HTML based help file hardcopy the form screen dump without further questions 1 1 to the printer generate a report for print export the current form into an MS Excel spreadsheet export the current form into pure ASCII text format convert the bibliographic reference ready for Cut amp Paste into other documents according to editorial guidelines of different journals open a cross table showing available mineral ligand combinations select all data records in the list cancel all data record selections in the list undo the last data modification inpu
65. etic data At pre sent there are no data records provided so it is up to the user to build his own data base Mineral Phases Original Select from scroll list Defaults to the mineral specified in the calling form Mineral Phases Product Select from scroll list In case that there are two or more product minerals select the more complicated one and put the others into the com ment field Chemical Reaction Equation Equation formulated with the original mineral phase being on the left hand side and the product mineral phase s being on the right hand side Chemical Reaction log beta Reaction constant related to the above formulated equation Chemical Reaction Reference Code Publication reference code about the above chemical reaction can be selected from a scroll list Kinetic Rate Law Equation Kinetic rate law for the above chemical equation in free format Kinetic Rate Law Parameters Values of up to three parameters of the above kinetic rate law Kinetic Rate Law Reference Code Publication reference code about the above ki netic rate law can be selected from a scroll list Comment Additional remarks 1 45 7 Administration This menu see Fig 25 combines several database management tasks some of them being only accessible to users with administrator privileges Respective buttons will be grayed out for other users REST Administration Daily Backup statistical Dat
66. ferring to Mera O TOUS 0 S Distribution of surface complexation constants records amongst lei bip Amount of surface complexation constants for actinides and relevant fission activation products contained in RES T ccccceeeeeeeeeeeees 1 Introduction 1 1 Problem World wide activities focus on the remediation of radioactively contaminated sites One common aim is to deliver a more profound chemical base for risk assessment namely all those physico chemical phenomena governing the contamination plume develop ment in time and space Coupled transport codes able to tackle this challenge have to simplify the resulting very complex reaction pattern To do so in an adequate way re quires to extend the knowledge about retardation and mobilization phenomena and the underlying basic processes and interactions such as physisorption chemisorption co precipitation inclusion diffusion surface precipitation or the formation of solid solu tions So far the physico chemical processes are considered if at all by applying conditional distribution coefficients Kg in order to model the partition of a contaminant between solid and aqueous phases The Kg is defined as the experimentally determined ratio of the sorbed fixed immobilized and non sorbed free truly dissolved fraction of a com ponent chemical element under equilibrium conditions The subsuming of many phys ico chemical processes into one purely phenomenological
67. field blank and specify all experimental ionic strengths in the comment field If there are mixed background electrolytes or ex periments with different electrolytes specify them in the comment field The type of the background electrolyte medium salt can be selected from a scroll list If not available go directly to the table Electrolyte there is no extra input mask available and add the respective medium Capacitances C1 and C2 Input in F m values given in other units should be con verted before with a respective addition to the comment field below depending on the SCM type one or both fields may stay empty The capacitance C2 when required by the triple layer SCM but not specified should be set to the default value of 0 2 F m Solid Liquid Ratio Input in g L values given in other units should be converted before with a respective addition to the comment field below SCM Type Select from a scroll list if not available go back to the Advanced Editing and add the respective model under Surface Complexation Model See there for de tails Fit Method Method software used to derive SCM parameters from the sorption ex periment Select from a scroll list If a method is not available go directly to the table Fitting there is no extra input mask available and add the respective method Add Edit Site Data The button will open an additional form Site Specific Data There site type specific data for bi
68. he right side of the mineral names Here the iron containing minerals ferrihydrite goethite hematite are selected see Fig 10 There are two buttons below the table that either select all checkbox button or none rubber button entries When all desired minerals are selected the Back button must be pushed to advance to the next step in the Data Assembly amp Formatting menu Selection of Minerals ayalite Ferrihwarite uorapatite unrite orsterite Ibbsite lauconite oethite rogsular ppum aematite ectorite edenbergite Hercynite Hydratalcite Hydroxplapatite lite Imogolite Jadeite EE Kine EVI Datensatz 14 4 1 ajal on 111 27 E Jap I 1 a1 o1 ind icd id kiz mi mik T lo 7 rbb id E E tl III ee g 5 gt Fig 10 Selection of minerals 5 2 Ligand Set Assembly An alphabetically sorted list of all ligands is presented where the user can make multi ple selections through the check boxes on the right side of the ligand names As an ex ample the heavy metals cadmium cobalt copper nickel lead and zinc were selected as sorbing contaminants see Fig 11 There are two buttons below the table that either select all checkbox button or none rubber button entries When all desired ligands are selected again the Back button must be pushed to advance to the next step in the Data Assembly amp Formatting menu 11 23 Sel
69. hemical structure model of the surface complex species as an image e g scanned from a publication Major Reference s List of publications dealing with the proof of existence of the above surface complex species The table shows the literature reference code au thors title and method dealt with for the publications Add Edit References The button will open an additional form Literature Species Evidence with the fields Species which defaults to the surface complex specified in the calling form Experiment where an experimental technique can be selected from a scroll list Reference where a publication reference code can be selected from a scroll list and Comments a place for any additional remarks Comment Additional remarks II 42 6 6 4 Ligand Definition This form see Fig 23 helps to define ligands i e all complexants capable of sorbing to mineral surfaces including not only contaminants but also matrix elements of any aqueous solution Formula JUO2 lt 2 gt Full Name uranyl1 Abbreviation Oxidation State E Charge 2 Molar Mass 270 028 ing mol Hadius 0 in nm Covalent or lonic Composition i hi T Fig 23 Advanced Editing form for the Datensatz M 108 et re von 113 ligand definition Formula Chemical formula of the ligand with the charge appended enclosed in sharp brackets Example UO2 lt 2 gt Cl lt 1 gt bipy lt 0 gt Full Na
70. ible through numeric iterations Also some long term effects that may render conventional distribution coefficients meaningless co precipitation dif fusion of trace elements into crystal lattices can be accounted for in a better way An other application is expressing Kp as a function of time related to better defined time dependencies of other basic parameters Furthermore it becomes possible to identify those parameters affecting the K strongest Consequently extra measurements can be designed efficiently to reduce its uncertainty And last but not least the formal keep ing of the used Ky paradigm renders it easy to couple a smart K framework with al ready existing contaminant transport and risk assessment codes enhancing its accep tance The unfolding of K values leads to the already mentioned Surface Complexation Mod els SCM This requires the definition of surface sites with a finite concentration Usu ally such surface sites are represented as XOH groups with X denoting a metal from the solid structure located at the solid liquid interface Many mineral surfaces but es pecially colloids carry a significant surface charge creating an electrostatic potential I 14 extending into the aqueous solution Depending of the charge of the ions they are ei ther attracted or repelled thus greatly influencing the sorption behavior of charged species and due to dipolar effects even neutral species To account in a proper
71. impor tant activity aims at automatic data conversion between various reaction formulations to account for the different formulations for chemical master species used in speciation 1 38 codes To close at least in a preliminary way data gaps future database releases should be supplemented by data estimation methods such as Linear Free Energy Rela tionships see e g Dzombak and Morel 1990 Also a future incorporation of data about the surface reactivity of the various crystal planes is anticipated To enlarge the application fields of RES T by a coupling to sorption databases utilizing the K approach namely the SODA database by Brasser ef al 2002 would generate further benefits A respective project proposal has been developed recently Whereas it has never been a goal of the present project to include also all the raw ex perimental data from sorption studies this has been frequently demanded by the user community In particular this eventually would enable the users to perform their own fit ting exercises to derive model parameters Such a task however would require much larger personnel and time resources than currently assigned to the project This also holds for a large scale incorporation of kinetic data and information of independent spectroscopic evidence for surface species despite the fact that the corresponding ta ble structures and input forms are already available To approach such a challenging task probably a
72. in the software and pro vide regularly updates of the database reflecting user response bug reports and requests for additional functionality and project progress based on the steadily ongoing development in the field of surface complexation and related sorption phenomena development in theories and models advance of experi mental methods The access to the database is controlled through user IDs and respective passwords The assignment of users to the various groups and the provision of valid passwords is organized by the authors of the database At present the user ID and the associated password will be sent by E mail Each user should have received one already if not please contact the RES T authors see end of this document for contact details II 8 2 Installation 2 1 RES T Software Package Based on the above explained authorization philosophy the following files are part of the RES T distribution RES3T_2000 mdb MS Access 2000 version of the database RES3T_Group mdw file for user authorization maintenance RES3T ini example template for local initialization file RES3T_Icon ico icon for the RES T application RES3T Readme pdf Readme file in Adobe PDF Format RES3T_Manual pdf this document in Adobe PDF Format 2 2 Minimal System Requirements The minimal system requirements to install and run RES T are An IBM PC compatible PC with Pentium or higher processor 64 MB of RAM 20 MB of free hard disk space CD ROM drive
73. ineral Such an ion also can be the proton H The reaction parameter K actually measures the competi tion between two ions MA initially occupying the site and Mg replacing ion for a sur face site therefore Kex is also called selectivity coefficient I 13 a M XOH M 8 Ko M XOH M 2 3 Surface Complexation Models SCM 2 3 1 Basic Principles To enable a thermodynamic consistent treatment of sorption requires the decomposi tion of the overall phenomenon into the main basic processes defining it Such an ap proach will unfold the single distribution coefficient into a vector of parameters such as Eu pH concentrations of the various components binding site densities surface ar eas and temperature Apparently this is a step backwards introducing a high degree of complexity and sig nificantly increasing the number of parameters But it has the great advantage that all these parameters can be measured with more reliability and precision Knowing the functional relationships between these processes and how they contribute to the Kg al lows a computation of latter rather than a measurement Moreover simulations with variable parameter values even for hypothetical conditions may easily yield a K sur face as a function of the primary parameter vector Kg f Eu pH pco T Usu ally the function f can not be expressed as an explicit function but contains implicit formulations only access
74. initions A mineral is an element of chemical compound that is normally crystal line and that has been formed as a result of geological processes Nickel 1995 Minerals are naturally occurring inorganic substances with a definite and predictable chemical composition and physical properties O Donoghue 1990 A mineral is a naturally occurring homogeneous solid inorganically formed with a definite chemical composition and an ordered atomic ar rangement Mason et al 1968 These minerals can be distinguished from one another by individual characteristics that arise directly from the kinds of atoms they contain and the arrangements these atoms make inside them Sinkankas 1966 A mineral is a body produced by the processes of inorganic nature having usually a definite chemical composition and if formed under fa vorable conditions a certain characteristic atomic structure which is ex pressed in its crystalline form and other physical properties Dana amp Ford 1932 See also the IMA Commission On New Minerals And Mineral Names Proce dures and Guidelines on Mineral Nomenclature Nickel and Grice 1998 for a technical discussion on what is a mineral In RES T the first definition is fol lowed How to deal with inconsistent contradictory data The original published value is stored in the database anyway but respective annotations have to be put into the comment field Furthermore set the status field to
75. ion type strong weak affinity tetrahedral octahedral coordination etc protolysis constants applied SCM type capaci tance values ion exchange capacity e Chemical ligands aqueous components ions master species which can be both inorganic or organic ones constituting elements stoichiometry charge radius redox state molar mass e Surface complexes species experimental e g spectroscopic or theory based evidence reaction equation formation constant chemical structure For any value the experimental method used to derive this value is stored together with the respective ionic strength and background media as well as any other informa tion necessary to evaluate the data or to calculate other derivative values If published uncertainty limits for numerical data are included This is a prerequisite for sensitivity 1 24 and uncertainty analysis In addition to the hard experimental results and parameters an extensive bibliography is provided too Every stored data item is linked to both origi nal citations and secondary literature references The references also comprise model evaluations with respect to theoretical limitations thermodynamic consistency and pa rameter sensitivity Moreover they cover questions of experimental design and inter pretation of results from sorption experiments or experimental methods used for such investigations with their associated error ranges and application areas All this
76. ith UD2 lt 2 gt as major ligand SCH Chemical log E Literature Type Equation Exp Norm Heference iD alU U4e E OL O42 r PTBP388 DL Pl Si OH U02 lt 2 gt H20 Si 0 UO02 0H 2 H lt 1 gt 5 6 37 r PTBF88 T oo 5H 300226 5H20 sSHOHUDOZBOHE 8Hcl 1678 17 47 P PTBP38 DDL r 2 s5 0H U02 lt 2 gt s5H0 2 UU2 Double Click For Details 551 591 r AZENO SEX DE ppL r ssibH U02 2e sSrD U02 1e H lt 1 gt 1 02 r PJTPO r JTFO1 T um is co Cc m 7 ii DL r s5 DH UD2 2 e 3H20 s5HD JD2 1e 4 Hel 19 42 DL r 2 S 0H UD2 2 51 0 2 102 2 Hc es r sSijwFOH U02 lt 2 H20 sSipsFO UO2 DH 2H 1e 464 592 1 r sSitwFOH U 2 2 H20 sSiwHO UD2 DH 2H 1e 5 28 656 rl r sSisH H U02 lt 2 gt H20 Sifs O U02 0H 2 Hed es 2 561 5 60 r sSitsrOH U02 lt 2 gt H2003 sSipsHDHID2CO3c1 3H 14 amp 50 778 NE r sSij HFOH UD2 2 H20 sSips IIO 2 DH 2 H lt 1 gt 4 395 5 22 ml lala m mr rat Bras ol nisus E amado i212 3p ala j D ala U A I EE a i m m m Ipkm E ajaj Fig 6 Query results of surface m complexation data for Quartz with UO Datensatz 14 5 LALI Surface Complex Formation all data records This button lists surface complex formation constants for the select
77. l additional databases e g about rocks and soils or with crystallographic information The programming of the database functionality has been enhanced by means of the Visual Basic for Appli cation VBA programming language 3 2 Information Coverage The database covers all the main surface complexation models in use at present dis criminating from each other by the way they handle electrostatic contributions to the Gibbs Free Energy of surface complex formation e Non Electrostatic Model NE e Diffuse Double Layer Model DDL e Constant Capacitance Model CC e Triple Layer Model TL e Basic Stern Model BS e 1 pK approach Charge Distribution Multisite Complexation Model CD MUSIC and 1 pK Basic Stern 1 pK BS I 22 LUNIA al T T 2140113939 juu AAD UJ ALID AD sasn SJEQUOEIYIPOR sn jeJs juauiua uses AL LO AL ESI LUMP S 360345310 ada LOS pau juaunadx3 ls 301 443 Do uonenbg 003044449075 433244905 211514305 ada ais 24305 puebr7 144805 Tpuebr sanads jee das JOA dEPpuosas Jeeuibiacm 2421114 dar JULIO je jua yunass 40323135 SSB AE OL snipe g xopa abet WAUOUAS AWER enun EEE Aysuagug jue aaa an addins E Jas al JP2QUOYeSIJIpoL RETE EN LL juauiua 415 juan LUNIA SIUSPIA 3 404 bus suo 460740 2 qoedes 515407044404 I 32ede2 Aysuare15404 ad Los Ea jo Zd LALO PUSS pa
78. lectrolyte medium salt can be selected from a scroll list If not available go back to the table Electrolyte there is no extra input mask available and add the respective medium Ligand is Itself Background Electrolyte Check this box if the above specified reac tion concerns either anion or cation of the background electrolyte This is only relevant for the triple layer and the 1pK SCM therefore this check box is grayed out for all other SCM selections Log K References for Electrolyte Anion Cation These two scroll lists only ap pear for triple layer and the 1pK SCM data records provided the check box for the background electrolyte is not checked Here the respective references to the back ground electrolyte reaction data can be selected The lists comprise of the publication reference code the already covered anions or cations and the RID unique reaction data record identifier The latter is important when a publication contains more than one different background electrolyte reaction data set for a given combination of min eral and ion type It is advisable to first put in the two records for the background elec trolyte so that these entries are already available for selection when it comes to the other surface complexes Comment Additional remarks about experimental details such as raw data reference code ionic strength of background electrolyte if experiments for various ionic strength are reported log K for o
79. me Full name of the ligand Abbreviation Short form of the ligand name e g in case of organic ligands such as NTA EDTA etc Oxidation State Only useful for ligands with central atoms metals having uniform oxidation states Not applicable to mixed redox compounds and most of the organic ligands Charge Formal charge of the ligand according to the above specified formula Molar Mass Molar mass of the ligand in mol g in the form as specified in the Com position table This value is automatically computed and can not be edited Radius lonic or covalent radius of the ligand not used so far Composition Table for the chemical composition of the ligand i e elements and their stoichiometric coefficients 11 43 Edit Stoichiometry The button will open an additional form Composition of Ligands with the fields Ligand which defaults to the ligand specified in the calling form Ele ment where a chemical element can be selected from a scroll list and Stoichiomet ric Coefficient where the respective stoichiometric coefficient must be entered 6 6 5 Surface Site Types This form see Fig 24 is used to define the relation between minerals and surface site types i e which surface site types can be assigned to a mineral S te Type stoichiometric 1 Coefficient Site Type esiw J OH Stoichiometric 1 Coefficient E Site Type Sil3 H gt Stoichiometric 1 Coefficient Site Type
80. means a transition from a pure data collection towards a smart database which ultimately will turn into a sorption expert system This purpose is supported by the already broad va riety of user interactions offered 3 3 User Interaction Instead of just being a printed collection of sorption data the computer based rela tional database opens additional opportunities of data processing by potential users The database contains a graphical user interface with two classes of hierarchical forms The first class serves for data input and editing the second one enables the se lection viewing and exporting of specific data sets To prevent unauthorized data ma nipulation and the emergence of different unsynchronized database versions the whole editing shell can be uncoupled and hidden from the user This is the default case leaving the following opportunities for user database interactions e Users can easily extract specific data sets e g all records relevant for the com bination of a specific mineral and a specific SCM e They can also choose to show all sorption data available for a certain element ligand ion or all published surface area data of a mineral e Once a data set has been generated it can be shown on the screen or printed out e Data selection can be exported in a file to be used in other geochemical speci ation codes Actually this is possible as Excel spread sheet or ASCII file e Original bibliographic
81. mineral specific and based on the concept of sur face complexation Surface Complexation Modeling SCM This concept is able to substitute distribution coefficients Ky values and to improve considerably the charac terization of sorption processes Accuracy and reliability of contaminant transport prog nosis are increased thereby An integrated user interface helps to access selected mineral and sorption data to ex tract internally consistent data sets for sorption modeling and to export them in formats suitable for other modeling software Data records comprise mineral properties specific surface area values surface binding sites characteristics sorption ligand information and surface complexation reactions The content of the database is very diverse and comprehensive Based on 1460 litera ture references data records for 111 minerals 879 sample specific data 1047 protoly sis data records and 2611 surface complexation constants are stored inside RES T as of July 31 2004 The elements covered by RES T comprises the actinides and fission products as well as the heavy metals and As but also major constituents of the background media groundwater seepage water solutions from corrosion processes Zusammenfassung Es wurde eine unter MS Access implementierte digitale thermodynamische Sorptions datenbank entwickelt und getestet Die Datenbank mit dem Namen RES T Rossen dorf Expert System for Surface and Sorption Thermody
82. mum therefore the Diffuse Double Layer model is selected to account for electrostatics The calculations were performed with the FITEQL code version 3 2 Herbelin and Westall 1996 In most cases the model prediction represented the experimental values for the sorbed amount of Np U Se and Cu expressed as conventional distribution coefficients Ky as required by Performance Assessment PA software within one order of magnitude or better As an example to illustrate the effect of parameter uncertainty in blind predictions the Np V sorption onto hematite was selected None of the randomly generated pK sets parameter at the uncertainty analysis did deliver unacceptable blind predictions for the distribution coefficients The vast majority of measured K values were predicted within one order of magnitude Thus the formally large spreading of the pK values as ex tracted from literature even after normalization and extrapolation to infinite dilution is actually not critical For well defined mineral systems provided a suitable database is accessible the SCM approach seems to be very promising This will be confirmed by further studies extending the range of minerals and contaminants 1 37 6 3 Benefit and Utilization The mineral specific thermodynamic sorption database RES T enables methodical pro gress in the e supply and valuation of thermodynamic sorption data e modeling of sorption processes for complex systems In combi
83. n OH 2 0 H Site Site Density in El pK SCH Literature Type sites nm Exp Horm Exp Horm PZC C1 Type Reference ERE ET 2 50 TIELE oH Ff sSHIH r 5i OH 50H eStOH T DH T estOH Dd 330 338 330 338 300 1 s5HUH 330 11 30 10773017 4 ee i Ea 1 c 7 1 IT ca gt 212 750 7 91 33 r 1pK B5 T MSHVBSE n d asof 368 7 50 768 200 33r Hw90 al r 5535a Fig 4 Query rHvB83a results of site E density and a surface protolysis data for Quartz Pol col col mlm m Alo on en en a i3 9 919 3 3 m cio o a a x Cy coy co D Poy ra cr el or I pla fala loja fa gt C ue hk ai Datensatz 14 4 por nre von 54 4 rai As clearly pointed out by Kulik 2002 the establishment of standard and reference states for surface complexation data is essential for a proper thermodynamic handling of such reactions Therefore a respective normalization procedure has been integrated into RES T allowing a comparison of the various SCM parameters for given combina tions of SCM subtype and mineral Following Kulik and setting the reference site den sity to 12 05 sites nm 20mmol m the protolysis constants are normalized ac cording the following equations where Tex is the experimentally determined surface site density exp exp 12 05 PK1 om PK1 xp log pK2 pK2 lo
84. n Database SCM have a high potential to increase confidence in performance assessment PA studies e They can partially replace Ky in simple systems It is possible to verify and check measured Ky values The most sensitive experimental parameters can be identified It is possible to assign uncertainty limits Gaps difficult to access in sorption experiments can be filled by computed val ues SOM helps to gain a better process understanding Furthermore the SCM concept combined with a powerful sorption database allows a straightforward extension towards rocks and soils composed of several minerals Their sorption behavior should be predictable from the weighted superposition of the sorption processes for all constituting minerals This has already been successfully demon strated by e g Gibb and Koopal 1990 Davis et al 1998 or Arnold et al 2001 The number of really important minerals is limited since about 20 minerals and mineral groups form more then 95 of the known rocks forming the earth s crust Ronov and Yaroshevsky 1967 Thus the sorption database will be of great benefit for the model ing of complex solids considerably expanding the application field of thermodynamic sorption models To support the above approach a digital thermodynamic database for surface com plexation equilibria is essential Unfortunately at present there is no such database available world wide only Kg compilations like
85. namics ist mineralspezifisch und basiert auf dem Konzept der Oberfl chenkomplexierung Surface Complexation Modeling SCM Dieses Konzept kann Verteilungskoeffizienten K Werte ersetzen und die Beschreibung von Sorptionsprozessen wesentlich verbessern Genauigkeit und Verl lichkeit von Prognosen zur Schadstoffausbreitung werden dadurch erh ht Eine integrierte Nutzer Schnittstelle unterst tzt den Zugriff auf ausgew hlte Mineral und Sorptionsdaten die Auswahl konsistenter Datens tze f r die Modellierung der Sorption und den Export in f r andere Modellierungssoftware geeignete Formate Die Datens tze umfassen Informationen zu Mineraleigenschaften spezifische Oberfl che Oberfl chenbindungsstellen sorbierenden Liganden sowie Oberfl chenkomplexie rungsreaktionen Der Inhalt der Datenbank ist sehr breitgef chert und umfassend Basierend auf 1460 Literaturreferenzen sind Datens tze f r 111 Minerale 879 probenspezifische Daten 1047 Protolysedaten und 2611 Oberfl chenkomplexierungskonstanten in RES T er fasst Die in RES T enthaltenen Elemente umfassen sowohl Actiniden und Spaltprodukte als auch Schwermetalle und Arsen sowie die Hauptbestandteile der Hintergrundmedien Grundwasser Sickerwasser L sungen aus Korrosionsprozessen CONTENT T INTRODUCTION ona aan 7 1 1 PEODIGI iii aos 7 1 2 Need or Sorpu1on Database en RUINIS 8 1 3 CG AIS rinnen 9 1 4 Users and Cooperatie ra oae ite iren eiie oa ie aee toii eese ep
86. nation the results allow a considerably more realistic and trustworthy descrip tion of speciation and migration of different contaminants e g radionuclides heavy metals arsenic The scientific technical benefit composed of first time central provision of most SCM data published in the open literature e plausibility and consistency check based on original literature with backtracking of secondary references e creation of fundamentals for validation of data sets regarding experimental er rors consistency and model adequacy as well as their representation for the respective minerals e output of sorption data sets flexible format fast convenient e automation of data processing with transfer of specially produced data sets in EXCEL and ASCII format e provision of tools for conversion and computation to increase the efficiency and decrease the error possibilities and identification of essential data gaps errors and discrepancies supporting the planning and optimization of further experimental investigations The database is publicly available as CD ROM or per e mail as ZIP File res3t fz rossendorf de bundled with an installation help and an extensive manual 6 4 Outlook The current status of the RES T database opens the way for several future develop ment directions One major goal is the implementation of a world wide web WWW gateway to allow easy external access to the data base via the Internet Another
87. nd Interface Science 63 480 499 Davis J A and Kent D B 1990 Surface complexation modeling in aqueous geo chemistry In Mineral Water Interface Geochemistry Reviews in Mineralogy Vol 23 Ed Hochella M F und White A F Mineralogical Society of America Washington D C p 177 258 Davis J A and Leckie J O 1978 Surface ionization and complexation at the oxide water interface ll Surface properties of amorphous iron oxyhydroxide and adsorp tion of metal ions Journal of Colloid and Interface Science 67 90 107 Davis J A Coston J A Kent D B and Fuller C C 1998 Application of the surface complexation concept to complex mineral assemblages Environmental Science amp Technology 32 2820 2828 Dzombak D A and Morel F M M 1990 Surface complexation modeling Hydrous ferric oxide Wiley New York l 42 Dzombak D A and Hudson R J M 1995 Ion exchange The contributions of dif fuse layer sorption and surface complexation In Aquatic Chemistry Interfacial and interspecies processes Advances in Chemistry Series 244 59 94 Felmy A R Girvin D C und Jenne E A 1984 MINTEQ A computer program for calculating aqueous geochemical equilibria EPA 600 3 84 032 Office Res Dev USEPA Athens GA Freundlich G 1906 ber die Adsorption in L sungen Zeitschrift f r physikalische Chemie 57 385 470 Gibb A W M and Koopal L K J 1990 Electrochemistry of a model for
88. nd guidelines on mineral nomenclature The Canadian Mineralogist 36 1 14 O Donoghue M 1990 American nature guides Rocks and minerals Gallery Books New York 224 p Parkhurst D L and Appelo C A J 1999 User s guide to PHREEQC Version 2 A computer program for speciation batch reaction one dimensional transport and in verse geochemical calculations U S Geological Survey Water Resources Investiga tions Report 99 4259 312 p Sinkankas J 1966 Mineralogy First course Van Nostrand Company Princeton New Jersey 587 p Steefel C I and Yabusaki S B 1995 OS3D GIMRT Software for modeling multi component multidimensional reactive transport User manual amp programmer s guide version 1 0 Battelle Memorial Institute II 51
89. nding site densities and surface protolysis constants accompanied by their respective uncertainties if available can be specified If a surface site type is not available yet for a certain mineral one has to go to the Advanced Edit ing menu and assign this site type under Surface Site Types to the respective min eral See there for details The generic site types should only be used when it is not clear which site type is meant by the authors II 35 The surface protolysis constants for 2pK models are defined as follows XOH 3 gt XOH H pK1 log K of 1 deprotonation step XOH gt XO H pK2 log K of 2 deprotonation step For an 1pK model as CD MUSIC only one protolysis constant is calculated which should then be inserted in the pK1 field XOH lt gt XOH 4H Experimental Method Original data source for the derivation of surface site densities SSD and protolysis constants pK This is not necessarily an experimental technique but could also just be a value taken from the literature from a single reference or as a weighted average or be computed based on crystallographic data or other theoretical considerations Select from a scroll list if not available go back to Advanced Editing and add the respective method under Experimental Method See there for details In The unit for the surface site density values should always be the original one an in ternal conversion to sites nm is
90. ned from various textbooks Dzombak and Morel 1990 Stumm 1992 Sposito 1984 and publications Davies et al 1978 Davies and Leckie 1978 Sposito 1983 Sposito 1989 Davies and Kent 1990 Goldberg 1995 Whereas the simplest and older sorption models do not distinguish between the vari ous processes outlined above that contribute to the overall sorption newer model ap proaches at least describe separately the effects of the electrostatic attraction between a surface and an ion having charges of opposite sign and the effects coming from a chemical reaction of an ion with a reactive surface site Therefore the sorption models are usually grouped into altogether three classes the phenomenological models and the surface complexation models with the latter comprising of electrostatic and non electrostatic models For all the formulae the following conventions apply Brackets specify concentra tions in mol L braces specify free activities in mol L M stands for a metal spe cies pure cation hydrolytic or complex species that can sorb onto a surface XOH denotes the protonated unreacted sorption site The activity coefficient dimension de pends on reaction equation of a species i is given by yi l 11 2 2 Phenomenological Models 2 2 1 Distribution Coefficient K Model The partitioning of dissolved ions between the solution and all relevant surfaces is gen erally characterized by the equilibrium
91. ns as entry ManualPath Either entries must not contain a trailing slash or backslash The file name pointing to the correct HTML page is internally derived from the StatusBarText property of the HelpButton in all respective forms 7 3 Export to MySQL Pressing the button Export to MySQL creates a script for use with the Open Source database MySQL This script is named esql add txt and is placed in the directory specified under the entry MySQLPath in the local options The local options contain also the name of the MySQL database to be created to be found under the entry MySQLDatabaseName The script esql_add txt is pure ASCII It creates all required tables and fills them with the appropriate data records lt does however neither mi grate the internal relationships between the tables nor keep all the queries forms macros and VBA modules used by MS Access This button is not activated for users without administrative privileges The SQL export routine is designed to follow as close as possible the international SQL standard As a result recently the RES T database was also successfully converted into an Oracle 9i database 7 6 Reload Local Options Pressing this button shows the current settings for several paths for programs or direc tories They are required by RES T but depend on the specific local PC installation RES T is running on These settings are read from a local initialization file and can be re loaded
92. nsities given in units of mol mol solid mol mol metal ion and mol g metal ion Mineral Group Select from a scroll list The categories are based on the chemistry and structure of the minerals namely the dominating anion lf a mineral group is not available it can be added directly in the table MineralGroup there is no extra input mask available Mineral Series Select from a scroll list The categories are based on petrologic con siderations If a mineral series is not available it can be added directly in the table MineralSeries there is no extra input mask available Molar Mass Molar mass for the above given formula in mol g Density Mineral density in g cm can be given as a range II 31 Add Edit Reactions The button will open an additional form Mineral Alteration and Kinetics There respective mineral reactions can be specified This form is also accessible through the Advanced Editing menu See there for further details Comment Additional remarks such as further alternative formulae modifications occurrence being a solid solution end member etc 6 3 Sample Specific Data This form Fig 17 summarizes the information that characterizes the samples used in sorption experiments This includes sample origin preparation steps and analytical re sults Mineral uartz Orginal Publication rez Citation in natural C industrial C laboratory C unknown Supplier Pennsylvania
93. o access selected mineral and sorption data to extract internally consistent data sets for sorption modeling and to export them in formats suitable for other modeling software Data records comprise mineral properties specific surface area values surface binding sites characteristics sorption ligand information and sur face complexation reactions An extensive bibliography is included providing links not only to the above listed data but also to background information concerning surface complexation model theories evidence for surface species and sorption experimental techniques As described in detail in chapter 4 the content of the database is very diverse and comprehensive Based on 1460 literature references up to now data records for e 111 minerals e 879 sample specific data e 1047 protolysis data records and e 2611 surface complexation constants are stored inside RES T All these numbers are as of July 31 2004 The elements covered by RES T comprises the actinides and lanthanides as well as the heavy metals and As but also major constituents of the background media groundwater seepage water solutions from corrosion processes A statistical evalua tion of the available SCM data records reveals that at present the information supply provided through the open literature s very unbalanced concerning the requirements of risk assessment and site remediation Most SCM data are determined for the contami nants uranium c
94. oll list presenting the numerical value of SSA in m g and the publication reference code The relation be tween surface site density SSD and SSA falls into one of two categories A The SSD was determined independent from a value of the SSA e g by means of theoretical crystallographic considerations Then the user has later to specify an own SSA value in order to allow SSD conversions into other units B The SSD was determined together with a SSA value Then this value and the respective literature reference must be given in the database 11 34 PZC pH of the point of zero charge total charge of the surface is zero Sometimes are other values are also given should be noted in the comment field the PZNPC point of zero net proton charge pH of the point where the surface charge caused by only proton and hydroxyl adsorption is zero PZNC point of zero net charge pH of the point where the surface charge caused by adsorption of other ionic ligands is zero IEP isoelectric point some authors use it as synonym for PZC PPZC pristine point of zero charge pH at which the sum of negative and positive charge becomes zero lonic Strength of lonic strength of the background electrolyte in mol L If experi ments for various ionic strengths are reported specify the lowest one in this field and mention the other ones in the comment field If the reported protolysis constants refer to an extrapolated infinite dilution leave the
95. opper cadmium and lead but nearly no data are available for other actinides especially under reducing conditions Concerning the solid phases iron hydr oxides clays quartz varieties aluminum hydr oxides and titanium oxides are well represented whereas important rock forming mineral groups such as feldspars mica pyroxenes amphiboles or olivines have not been investigated to a satisfactory extent The largest data subsets are accumulated for the minerals Goethite a I 35 FeOOH Ferrihydrite Fe203 H20 Hematite a Fez03 amorphous Silica amp Quartz SiO2 Alumina y Al203 Kaolinite AlzSi205 OH 4 Vernadite 6 MnO Anatase amp Rutile TiO gt Montmorillonite Nao33Mgo 33Al1 67Si4010 OH 2 and Magnetite Fes3O The overwhelming majority of SCM data was determined at room temperature for any scenario coupled to elevated temperatures the database will be insufficient Here addi tional experiments and the development of reliable temperature extrapolation methods is Of paramount interest It is also interesting to analyze the experimental methods and the data processing pro cedures fitting methods codes mainly used to obtain SCM parameters The majority of the surface site density values originates from potentiometric titrations Other often used methods are the tritium exchange and sorption isotherms The potentiometric ti tration is the preferred experimental method for the calculation of the protolysis con
96. os vost tes 10 2 MODELS FOR THE DESCRIPTION OF SORPTION PHENOMENA 11 2 1 Fundamentals 11 2 2 Phenomenological Models eu 12 22 1 Distribution Coefficient Ka Model ooooonccnnnnnnnnnnonoccconononononanocccnnnnonnnnnons 12 222 Langmuir Adsorption Model ii a 12 229 Freundlich Adsorption Model a euin 13 2 2 4 Ion Exchange Model een ne 13 2 3 Surface Complexation Models SCM ssscsccssssssssscccscsssssscccsssssssscsseees 14 2 3 1 Basie Price DIS ee ee 14 ee Constant Capacitance Model nee en 16 23 3 Diffuse Double Layer Mode lerroartean aa n Ei 16 2 3 4 Triple Layer Modellen 17 235 Other Models une ne ai 19 2 3 6 Non Electrostatic Surface Complexation Model 20 3 DESIGN OF THE DATABASE aida 22 3 1 Structural Design Implementation eee eere eee eee eee eerte 22 3 2 Information Coveralia id 22 3 3 User Interaction ss rei 25 3 4 Intesrated Tools ua u 26 4 DATABASE CONTENT une 27 4 1 Publications uno 27 4 2 Minerals M Mn 27 4 3 sample Specific Data ae 28 4 4 Site Density and Surface Protolysis cccccccsssssssssssscccccsscssscssssscccesssseeees 28 4 5 5 5 1 5 2 5 3 5 4 5 5 6 6 1 6 2 6 3 6 4 6 5 7 8 Surface Complex Formation 29 DESCRIPTION OF THE DATABASE eene nennen nene 32 Data Query and
97. ournal of Colloid and Inter face Science Geochimica et Cosmochimica Acta and Environmental Science and Technology are the main source of SCM data Fig 6 shows the relative amount of pub lished SCM papers by the major journals Other important data source categories are books reports conference proceedings Ph D and M Sc thesis RES T database Major journals publishing SCM papers Others Journal of Colloid and Interface Science Radiochimica Acta Colloids and Surfaces A Soil Science Society Geochimica et of America Journal Environmental Cosmochimica Acta on Fig 6 Major journals echnology i publishing SCM papers 4 2 Minerals At present more than hundred minerals are available in the database They are cate gorized into several mineral groups based on the chemistry and structure of the miner als namely the dominating anion feldspars pyroxene amphibole mica olivine Fe oxides hydroxides Al ox ides hydroxides Mn oxides hydroxides other oxides clay minerals other sili cates Ti oxides carbonates quartz varieties phosphates others In parallel the minerals are also grouped into various series based on petrologic con siderations rock forming minerals 1 feldspar quartz rock forming minerals 2 pyroxene amphibole mica olivine rock forming minerals 3 others weathering minerals Fe Al Mn hydr oxides l 27 heavy minerals oxides no Fe Al Mn others clay minerals layer silicates
98. ovided for all surface complexation constants These demands are also guidelines for the structure imple mentation and utilization of the database for details see chapter 3 The result of the project is the RES T database the Rossendorf Expert System for Sur face and Sorption Thermodynamics 1 4 Users and Cooperation The announced users comprise e Scientific community with expertise on contaminant transport and waste man agement e Engineering companies and consultants e Risk assessment experts e Nuclear and chemical industry e Governmental authorities which are dealing with problems in e Storage and disposal of chemically toxic and radioactive wastes e Planning and maintaining of municipal waste disposals e Closure and remediation of mining influenced areas brown coal uranium ore copper schist phosphates etc e Safety measures monitoring and restoration of contaminated military bases and abandoned industrial facilities or e Prevention and emergency management of accident scenarios with release of contaminants For a successful migration of the RES T database to the announced users a maximum operator convenience is a must Therefore a straightforward unrestricted access to the database is coupled with a user friendly interface Over the entire term of the project there was a close cooperation with potential users Interested people and institutions got a preliminary version of the database e
99. patchwise heterogeneous surfaces The rutile hematite system Colloid and Interface Science 134 122 138 Goldberg S 1995 Use of surface complexation models in soil chemical systems In Advances in agronomy Vol 47 Ed Sparks D L Academic Press San Diego 233 329 Hayes K F Redden G Ela W and Leckie J O 1991 Surface Complexation Models An evaluation of model parameter estimation using FITEQL and oxide mineral titration data Journal of Colloid and Interface Science 142 448 469 Herbelin A L and Westall J C 1996 FITEQL Version 3 2 Report 96 01 Department of Chemistry Oregon State University Hiemstra T Van Riemsdijk W H und Bruggenwert M G M 1987 Proton adsorption mechanism at the gibbsite and the aluminium oxide solid solution interface Netherland Journal of Agricultural Science 35 281 293 Hiemstra T Van Riemsdijk W H und Bolt G H 1989 Multisite proton adsorption modeling at the solid solution interface of hydr oxides A new approach Model description and evaluation of intrinsic reaction constants Journal of Colloid and Interface Science 183 91 104 Hiemstra T und Van Riemsdijk W H 1996 A surface structural approach to ion adsorption The charge distribution CD model Journal of Colloid and Interface Science 179 488 508 Karpov I K Chudnenko K V und Kulik D A 1997 Modeling chemical mass transfer in geochemical processes Thermodynamic relations condi
100. r modeling software Data records comprise of mineral properties specific surface area values characteristics of surface binding sites and their protolysis sorption ligand information and surface complexation reactions The following sub models are already implemented extensions to other variants are straightforward the Non Electrostatic Model the Diffuse Double Layer Model the Con stant Capacitance Model the Triple Layer Model the Basic Stern Model and the 1 pK approach CD MUSIC For every SCM type where applicable also the concept of strong and weak binding sites is included Surface species composed from up to two different ligands can be incorporated An extensive bibliography is included providing links not only to the above listed data items but also to background information concerning surface complexation model theories related software for data processing and modeling and sorption experiment techniques Only very few of the abundant surface complexes proposed in the literature mostly resulting just from best fit considerations are actually validated by spectro scopic evidence or supported by theoretical quantum chemical calculations If such information is available it is also stored in the database The database will help to substitute the at present in risk assessment studies most of ten applied simplistic distribution coefficients K values by the more realistic descrip tion of sorption phenomena with SC
101. r s guide to PHREEQC Version 2 A computer program for speciation batch reaction one dimensional transport and inverse geochemical calculations U S Geological Survey Water Resources Investigations Report 99 4259 312 p Petschel M Lang G and Richter A 1995 Bestandsaufnahme und Bewertung des Datenmaterials von geochemischen Experimenten sowie Zusammenstellung in Form einer Datenbank zur Verwendung der geochemischen Modellierung Abschlussbericht zum BMBF Vorhaben 02 E 8573 IfE Leipzig GmbH Dresden Ronov A B and Yaroshevsky A A 1967 Chemical structure of the earth s crust Geochemistry International 4 1041 1066 Sahai N und Sverjensky D A 1998 GEOSURF A computer program for modeling adsorption on mineral surfaces in solution Computers and Geosciences 24 853 873 Schindler P W und Gamsj ger H 1972 Acid base reactions of the TiO2 Anatase water interface and the point of zero charge of TiO suspensions Kolloid Zeitschrift Zeitschrift f r Polymere 250 759 763 Sposito G 1983 On the surface complexation model of the oxide aqueous solution interface Journal of Colloid and Interface Science 91 329 340 oposito G 1984 The surface chemistry of soils Oxford University Press New York oposito G 1989 Surface reactions in natural aqueous colloidal systems Chimia 43 169 176 Steefel C l and Yabusaki S B 1995 OS3D GIMRT Software for modeling multicomponent m
102. r the vast majority of possible refer ence source types Access Copy Hard copy registration number for publications where a hard copy is available otherwise information about where to look for that publication is stored there For internal use only this field may be deleted hidden for external users in later revi SIONS Journal Title of the journal select from a scroll list This list is stored in the table Jour nals and can be edited there directly if necessary there is no extra input mask avail able Volume Volume of the journal This field may also contain the number registration code of reports then it is labeled Report No 11 29 Chapter Chapter of a book or report URL WWW link to online publications must be a valid URL and should start with http Book Title of the book or report including the subtitle and the edition number ISBN International registration number for books can be given with or without the usually used hyphens This field can also contain the ISSN number for regularly issued series Town Publishing place of the book Publisher Publisher of the book company or institution Editor s Editors of the book the input style is the same as for the authors Comment Further bibliographic information e g Dissertation Abstracts No remarks about duplications and contradictions wrong citations missing values missing refer ences to original raw data sources other pu
103. rption isotherm concept because this takes into consideration saturation effects due to the limited number of reactive surface sites that are really accessible in a reaction This surface site density however is a parameter not so easily to determine It can be obtained from measurements of maximum sorption values maximum proton uptake by tritium exchange methods or through theoretical considerations for details see Dzombak and Morel 1990 Values determined for the same surface may differ by a factor of two to three The surface site density is often given the symbol T with the units mol m or sites nm but also mol L solution mol mol metal or mol g solids are reported so care must be taken when using such values 2 2 3 Freundlich Adsorption Model The Freundlich model Freundlich 1906 again is very similar to the Ky approach as suming infinite numbers of surface sites The difference is that the reacting species M is assigned a mass action stoichiometric coefficient of 1 n XOH M 6 Ko o MI hy XOH The applicability of the model can also be checked through a linearized version of the above equation 7 log XOH M logK en n Other isotherms in use to a lesser amount are named after Toth Dubinin Radushkevich and Frumkin 2 2 4 lon Exchange Model This model Bolt 1979 Dzombak and Hudson 1995 describes the process of ex changing an ion from the solution with an ion on the surface of a m
104. s could be detected So identical complex stability constants are used which reduces the number of parameters somewhat for both site types Fortunately when dealing for sorption of contaminants in natural systems the concentration of contami nants is near to trace levels However in cases where the concentration of the sorbing ions is considerably larger surface precipitation may become important It is worthwhile to note that such precipitations onto a surface will already occur at concentrations be low the values that must be exceeded in the bulk solution because the solid activity on surfaces is less than unity I 15 2 3 2 Constant Capacitance Model The Constant Capacitance Model Schindler and Gamsj ger 1972 Hohl and Stumm 1976 assumes only one layer or plane o plane between surface and bulk solution All specifically adsorbed ions contribute to the surface charge in this layer The total charge o is computed using a constant capacitance term C according to 11 c CY O Actually the constant capacitance model is just a special case of the diffuse layer model for solutions of high ionic strength I gt 0 01 mol L and surfaces of low potential see especially Hayes et al 1991 It is strongly dependent from the ionic strength and requires one more parameter than the Diffuse Double Layer model The positioning of ions and the correlation between charge and potential is shown in Fig 1 Y Constan
105. t deletion of the current form update the display in the form after changing the content of underlying auxiliary tables close the form and bring you back to the previous form or menu functions also as OK button in input forms II 15 4 Data Query amp View This part of the RES T interface see Fig 2 ensures that users can easily extract spe cific data sets e g all records relevant for the combination of a specific mineral and a specific SCM They can also choose to show all sorption data available for a certain element ligand ion or all published surface area data of a mineral Once a data set has been generated based on queries it can be shown on the screen or printed out as a nicely formatted report The results can also be exported into MS Excel spreadsheets for further processing Double clicking into a scroll list of the query form after a valid selection will give access to all details of the respective query selection The only exception is the input field for the publication search string RES T Data Query amp View for a selected mineral Specific Surface Area site Density amp Surface Protolysis surface Complex Formation far a selected SCM or for a selected ligand gt ar all data records Publications for a selected authar or cada Fig 2 Data Query amp View menu of the RES T database ouch a more detailed look at data items is also provided in the various query
106. t Capicitance Model XOH XOH XO XOMe XL 9 O 5 N X 0 0 Oo Fig 1 Positioning of ions and correlation between charge and potential for the Constant Capacitance Model 2 3 3 Diffuse Double Layer Model In the Diffuse Double Layer Model Stumm ef al 1970 Dzombak and Morel 1990 the total charge o is defined by the following equation with all parameters being defined al ready before I 16 12 0 0 0 with O 0 11747 sin ZW AT An important advantage of this rather simple approach is that there are no electrostatic parameters required at all This reduces data needs and consequently data uncer tainty for a detailed discussion see Dzombak and Morel 1990 lonic strength de pendence is taken into account as long as is below 0 1 mol L However there are other cases where this approach can not be applied because of a more complex sur face chemistry The position of ions and the correlation between charge and potential is shown in Fig 2 T Diffuse Double Layer Model XOH XOH XO XOMe XL Diffuse Layer 0 0 Xq Oo Od Fig 2 Positioning of ions and correlation between charge and potential for the Diffuse Double Layer Model 2 3 4 Triple Layer Model In the Triple Layer Model Yates et al 1974 Davis et al 1978 two different planes are assumed for the surface The innermost or o plane does only incorporate protonation or deprotonation of surface sites All o
107. t used so far 5 4 Administration This menu combines several database management tasks some of them being only accessible to users with administrator privileges Respective buttons will be grayed out for other users These tasks are the backup of the whole database a statistical data evaluation the definition of an export format for bibliographic references the definition of the path to the online manual a routine exporting RES T into an SQL based file for I 33 use in other database software such as MySQL or Oracle and the management of various local options 5 5 General Help Pressing the button Help will open the start page of an HTML based RES T manual provided a web browser is already installed on the PC Inside the manual one can navi gate in the usual manner with all the menu screenshots providing click sensitive areas In addition to this general help most of the important menu forms also provide a help button in their footer section which will bring the user to a chapter of the online manual relevant for the respective menu form 1 34 6 Summary 6 1 Results An MS Access based digital thermodynamic sorption database has been developed and tested This database is named RES T Rossendorf Expert System for Surface and Sorption Thermodynamics It is mineral specific and can therefore be used for ad ditive models of complex solid phases such as rocks or soils An integrated user inter face helps users t
108. ther ionic strengths if values are not clearly assigned citation of values in other references formed complexes mono dentate bi dentate inner sphere outer sphere note if the stored values are recalculated ones etc 6 6 Advanced Editing The menu Advanced Editing see Fig 20 combines input masks for all auxiliary in formation that usually is not changed very frequently II 39 RES T Advanced Editing SCM Theory Experimental Methods Species Spectroscopic Evidence Ligand Definition Surface Site Types Mineral Alteration amp Kinetics Fig 20 Advanced Editing menu of the REST database 6 6 1 SCM Theory This menu see Fig 21 helps to maintain information about the various subtypes of surface complexation models in use lt should provide end users with some back ground knowledge about how to use and interpret SCM data Theory Triple Layer Acronym TL Major Reference s Add Edit References Modeling onc strength effects on cation adsorption at hydrous oxide solution Ibterra L aab L tzenkirchen J Parameter estimation for the triple layer model Analysis of conventional methods an Datensatz M 4 Comment Two capacitance parameters required TL is an extended Stern model see H80 amp Fig 21 Advanced Editing form for the SCM theory Datensatz 14 4 3 r gt von 11 Theory Full name of the SCM sub model theory 11 40 Acronym Acronym of SCM sub mo
109. ther specifically adsorbed ions are assigned to the outer or B plane Therefore each plane has its own charge and potential The third layer to justify the name of the model is as in the above models the diffuse layer See Fig 3 for a schematic picture The total charge for these three planes are computed from the respective capacitances C and potentials Y l 17 0 0 0 0 0 C pp PB Pp Og Co pg P C PP oO Csa CF Y 13 The charge og of the diffuse layer is for monovalent symmetric electrolytes given by the Gouy Chapman equation with the dielectric constant e und the permittivity in vacuum Eo 14 O amp RTI sinh xr Here we have thus two additional electrostatic parameters Co p and C4 often just re ferred as C4 and Co To reduce the number of variable model parameters C is often generally fixed to 0 2 whereas C is a fitting parameter inside a range between 0 1 and 2 0 which is supported by theoretical considerations XOH Triple Layer Model XOH A E K XOH m L XO Me XOH XO C4 Mice eed ME mM Ba m E Diffuse Layer 0 Xp Xq Oo Op Od Fig 3 Positioning of ions and correlation between charge and potential for the Triple Layer Model l 18 2 3 5 Other Models Basic Stern Model The Basic Stern Model Bowden et al 1977 Westall and Hohl 1980 perhaps can be considered as combination of Constant Capacitance and Diffuse Double
110. through this menu button after any changes therein The options define various directories to store exported files in MS Excel format MySQL format or pure ASCII text Here also the name of an exported MySQL file is specified the path to a locally installed simple text editor most often notepad exe and the path to the manual pages either a local one or a WWW link address Finally the name of a path for backups of the RES T tables is given These setting are loaded at start from an initialization file named res3t ini and placed in the local Windows system installation directory most often C WIN C WINNT or CAWINDOWS 11 48 In case there is no initialization file available the following default values will be loaded with WINDIR denoting the local Windows installation directory and TEMP denoting the local temporary directory both extracted automatically by RES T from the respec tive system environment variables e ManualPath Manual e NotePad WINDIR notepad exe e BackupPath TEMP Backup e ASCIIPath TEMP Export2ASCIl e ExcelPath TEMP Export2Excel e MySQLPath TEMP Export2MySQL e MySQLDatabaseName res3t Please ensure that these directories or the ones defined explicitly by the user in the initialization file are really existing Whereas the path pointing to the manual must be relative to the place where the RES T database itself is located the paths for the export directories ASCII MySQ
111. ti cal overview DOE Technical Report TR WSA 48 Bolt G H 1979 Soil chemistry B Physico chemical models Elsevier Amsterdam Bolt G H und Van Riemsdijk W H 1982 lon adsorption on organic variable charge constituents In Soil Chemistry B Physico chemical models Ed Bolt GH Elsevier Amsterdam 459 503 Bowden J W Posner A M und Quirk J P 1977 lonic adsorption on variable charge mineral surfaces Theoretical charge development and titration curves Aus tralian Journal of Soil Research 15 121 136 Bradbury M H und Baeyens B 1997 A mechanistic description of Ni and Zn sorp tion on Na Montmorillonite Part Il Modelling Journal of Contaminant Hydrology 27 223 248 Brasser T M nig J Scherschel C and Veerhoff M 2002 Sorptionsdatenbank SODA Datenbank zur Bestandsaufnahme und Bewertung geochemischer Informa tionen zum Verhalten von Abfallinhaltsstoffen im Deckgebirge einer UTD UTV Ab schlussbericht zum BMBF Vorhaben 02 C 06186 GRS 182 Gesellschaft f r Reak torsicherheit GRS mbH Braunschweig Brown P L Haworth A Sharland S M und Tweed C J 1988 HARPHRQ A geochemical speciation program based on PHREEQE Nirex Safety Studies Report NSS R188 UK Nirex Ltd Davis J A James R O and Leckie J O 1978 Surface ionization and complexa tion at the oxide water interface Computation of electrical double layer properties in simple electrolytes Journal of Colloid a
112. tions of equilibria and numerical algorithms American Journal of Science 297 767 806 Kulik D 2002 Sorption modelling by Gibbs energy minimisation Towards a uniform thermodynamic database for surface complexes of radionuclides Radiochimica Acta 90 815 832 Kurbatov M H Wood G B und Kurbatov J D 1951 Isothermal adsorption of cobalt from dilute solutions Journal of Physical Chemistry 55 1170 1182 Langmuir I 1916 The constitution and fundamental properties of solids and liquids Part Journal of American Chemical Society 38 2221 2295 Ludwig C 1996 A program for solving speciation problems Evaluation of equilibrium constants and other physical parameters University Bern sthols E 1994 The C Letagrop program system Version 1 4 Royal Institute of Technology Report TRITA OOK 2051 Stockholm Papelis C Hayes K F und Leckie J O 1988 HYDRAQL A computer program for the computation of chemical equilibrium composition of aqueous batch systems 43 including surface complexation modeling of ion adsorption at the oxide solution inter face Tech Rep No 306 Dep of Civil Eng Stanford Univ Stanford CA Parkhurst D L 1995 User s guide to PHREEQC A computer program for speciation reaction path advective transport and inverse geochemical calculations U S Geological Survey Water Resources Investigations Report 95 p 4227 Parkhurst D L and Appelo C A J 1999 Use
113. to RES T groupfile All four items in this command line are separated by space If any of the three paths contain spaces themselves you must include them into quotation marks An exam ple is given below adapt it to your needs please D MSOffice Office MSACCESS EXE IARES3T_2000 mdb Wrkgrp I RES3T_Group mdw Each time you start RES T e g by double clicking the icon created as described above you will be asked for your user ID and the password Both you should have received in a separate E mail To be able to export database research results into MS Excel or pure ASCII format the local path to the MS Windows notepad exe editor and the directories to store Excel and ASCII output files must be set These and other setting are loaded at start from an initialization file named res3t ini An example template for such an initialization file is provided and should be placed in the local Windows system in stallation directory most often C WIN C WINNT or C WINDOWS In case there is no initialization file available default values will be loaded see the chapter about Administration for details Please ensure that these default directories or the ones defined explicitly by you in the initialization file are really existing At present the online manual is only accessible as a local version with all HTML files placed in the subdirectory named Manual Therefore the path must simply be set to Man II 10 ual
114. u poygay yd pauspJ215 an Ag Jagse puoig Jepuibiam 24211114 cr JULIO 53141 a 340330435 enu al AJsuag ada 5154 0304 ar 21209115 a2uaa Jag SSP YOY Sauer Jpqui amp s AJaquunpJaluao3g Juana purr yauag JI quawajg pue JULIO SO Ep pou JI juan 30044 sanads dasn ajequoneauipop snqgejs qua potjyapjeadg aZIGUIEJE AMES Poy Jaydang auenJajduec WIG unorngedag Je Jepuasag Jeeuibiacm 243101114 Jas ajequonea porm 5n 235 jusunuo s40 1PJ LAO 43451 9Md Jequing p5 35T 4009 Tan Jajdeu anjo Sy gula N3do MESI 341144045 epi puis eure NNI 30d be 10J5 sabe 4th JESA SJOUING alejada Jade cr add jaded uojesjgndg juan salac eraut cr ETERNE juu sace Jap droe aJnjandq5e3s442 AjJsuar SSE AAE O EINWAOZ Eaa Lus auensibur3 JUSWUWWOT daoen cr ATA queo juan gan wagt dx ada parum ar Ja I 523 I amp ETT ad 2315 ips and content of the data tables of RES T ionsh Internal relati Fig 5 l 23 An extension to other models is possible For every SCM type where applicable the concept of strong and weak binding sites after Dzombak and Morel 1990 is included Surface species composed from up to two different ligands can be incorporated In general all parameters recorded in the database are traced back to the original pub lication incl
115. uding as many experimental details as possible to permit an evaluation of the data items All internal relationships of complex data sets are stored assuring a maximum of transparency and enabling the selection of internally consistent parameter sets Internal consistency means that a complete data set for a mineral surface and several aqueous complexing ligands ions is based upon the same values for the sur face binding site density utilizes the same surface complexation model applies identi cal site protolysis constants and if applicable the same electric capacitance values It also means that together with any reaction constant the original ionic strength and medium must be stored to allow later extrapolations to other desired conditions In a strict sense even the pertinent aqueous speciation pattern in equilibrium with the sur face complexes at the experimental conditions should be recorded which is at the moment not implemented yet however The data records contain information about e Minerals English names official and trivial ones formula density molar mass reaction paths aging weathering formation of secondary phases with the ap propriate reaction products chemical equation and thermodynamic and kinetic constants e Mineral surface properties sample specific specific surface area with associ ated grain size fraction point of zero charge origin and treatment of the solid e Surface binding sites concentrat
116. ultidimensional reactive transport User manual amp programmer s guide version 1 0 Battelle Memorial Institute Stumm W Huang C P und Jenkins S R 1970 Specific chemical interaction affecting the stability of dispersed systems Croatica Chemica Acta 42 223 245 Stumm W 1992 Chemistry of the solid water interface Wiley New York Ticknor K V and R egger B 1989 A guide to the NEA s sorption data base Version 2 0 OECD NEA Paris Van der Lee J 2003 CHESS The Assistant for Chemists and Engineers http chess ensmp fr Westall J C 1979a MICROQL I A chemical equilibrium program in BASIC Tech Rep Swiss Federal Institute of Technology EAWAG Dubendorf Switzerland Westall J C 1979b MICROQL Il Computation of adsorption equilibria in BASIC Tech Rep Swiss Federal Institute of Technology EAWAG Dubendorf Switzerland Westall J C 1982 FITEQL A computer program for determination of equilibrium constants from experimental data Rep 82 01 Department of Chemistry Oregon State University Corvallis OR 1 44 e Westall J C und Hohl H 1980 A comparison of electrostatic models for the ox ide solution interface Advances in Colloid and Interface Science 12 265 294 e Westall J C Zachary J L und Morel F M M 1976 MINEQL A computer program for the calculation of chemical equilibrium composition of aqueous systems Tech Rep Note 18 Ralph M Parsons Lab Dep Civil
117. z rossendorf de FWR VB I 50 11 References Allison J D Brown D S and Novo Gradac K J 1991 MINTEQA2 PRODEFA2 a geochemical assessment model for environmental systems Version 3 0 user s man ual Report EPA 600 3 91 021 U S Environmental Protection Agency Environ mental Research Laboratory 106 p Bennett D G Liew S K Mawbey C S and Read D 1992 CHEMTARD theo retical overview DOE Technical Report TR WSA 48 Brown P L Haworth A Sharland S M and Tweed C J 1988 HARPHRO A geochemical speciation program based on PHREEQE UK Nirex Ltd Nirex Safety Studies Report NSS R188 Dana E S and Ford W E 1932 A textbook of mineralogy 4 edition John Wiley amp Sons New York 851 p Karpov I K Chudnenko K V and Kulik D A 1997 Modeling chemical mass transfer in geochemical processes Thermodynamic relations conditions of equilibria and numerical algorithms American Journal of Science 297 767 806 Kulik D 2002 Sorption modelling by Gibbs energy minimisation Towards a uni form thermodynamic database for surface complexes of radionuclides Radiochimica Acta 90 815 832 Mason B and Berry L G 1998 Elements of mineralogy W H Freeman and Com pany San Francisco 550 p Nickel E H 1995 The definition of a mineral The Canadian Mineralogist 33 689 690 Nickel E H and Grice J D 1998 The IMA Commission on new minerals and min eral names Procedures a

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